Pesticidal Active Mixtures Comprising Aminothiazoline Compounds

ABSTRACT

Pesticidal mixtures comprising aminothiazoline compounds The present invention relates to pesticidal mixtures comprising as active compounds 1) at least one aminothiazoline compound I of the Formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are defined in the description; and 2) at least one active compound II selected from a group A comprising acetylcholine esterase inhibitors, GABA-gated chloride channel antagonists, sodium channel modulators, nicotinic acetylcholine receptor agonists/antagonists, chloride channel activators, juvenile hormone mimics, compounds affecting the oxidative phosphorylation, inhibitors of the chitin biosynthesis, moulting disruptors, inhibitors of the MET, voltage-dependent sodium channelblockers, inhibitors of the lipidsynthesis and other compounds as defined in the description, in synergistically effective amounts. The invention relates further to methods and use of these mixtures for combating insects, arachnids or nematodes in and on plants, and for protecting such plants being infested with pests, especially also for protecting seeds.

The present invention relates to pesticidal mixtures comprising as active compounds

1) at least one aminothiazoline compound I of formula I:

-   -   wherein     -   R¹ is selected from hydrogen, COCH₃, COCH₂OCH₃, COCH₂CH₃ or         COCH₂C(CH₃)₃;     -   R² is selected from fluoro, chloro, bromo, CF₃, CH₃ or CH₃O,     -   R³ is selected from hydrogen, fluoro, chloro, bromo, CF₃ or CH₃,     -   or     -   R² and R³ form together with —OCF₂O— or —O—CH₂—O— a 5-membered         fused heterocyclic ring;     -   R⁴ is selected from hydrogen, fluoro, chloro, bromo, CF₃, CH₃O         or CH₃;     -   R⁵, R⁶ are selected from hydrogen, chloro, fluoro, bromo, CH₃,         CH₃O or CF₃, wherein at least one of R⁵ or R⁶ is not hydrogen;         or the tautomers, enantiomers, diastereomers or salts thereof,         and         2) at least one active compound II selected from group A         consisting of         A.1 Acetylcholine esterase inhibitors selected from triazemate         or from the class of carbamates consisting of aldicarb,         alanycarb, benfuracarb, carbaryl, carbofuran, carbosulfan,         methiocarb, methomyl, oxamyl, primicarb, propoxur and thiodicarb         or from the class of organophosphates consisting of acephate,         azinphos-ethyl, azinphos-methyl, chlorfenvinphos, chlorpyrifos,         chlorpyrifos-methyl, demeton-S-methyl, diazinon,         dichlor-vos/DDVP, dicrotophos, dimethoate, disulfoton, ethion,         fenitrothion, fenthion, isoxathion, malathion, methamidaphos,         methidathion, mevinphos, monocrotophos, oxymethoate,         oxydemeton-methyl, parathion, parathion-methyl, phenthoate,         phorate, phosalone, phosmet, phosphamidon, pirimiphos-methyl,         quinalphos, terbufos, tetrachlorvinphos, triazophos and         trichlorfon;         A.2 GABA-gated chloride channel antagonists selected from the         cyclodiene organochlorine endosulfan, from         N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)         hydrazon or         N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl)         hydrazon or from the class of phenylpyrazoles consisting of         acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole,         vaniliprole and the phenylpyrazole compound II.A^(2.1):

A.3 Sodium channel modulators selected from the class of pyrethroids consisting of allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, permethrin, silafluofen and tralomethrin; A.4 Nicotinic acetylcholine receptor agonists/antagonists selected from nicotin, cartap hydrochloride or thiocyclam or selected from the class of neonicotinoids consisting of acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam and AKD-1022; or selected from the allosteric nicotinic acetylcholine receptor agonist spinosad; A.5 Chloride channel activators selected from abamectin, emamectin benzoate, lepimectin or milbemectin; A.6 Juvenile hormone mimics selected from hydroprene, kinoprene, fenoxycarb or pyriproxyfen; A.7 Compounds affecting the oxidative phosphorylation selected from diafenthiuron, fenbutatin oxide, propargite or chlorfenapyr; A.8 Inhibitors of the chitin biosynthesis selected from buprofezin or from the class of benzylureas consisting of bistrifluoron, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, novaluron or teflubenzuron; A.9 Moulting disruptors selected from cyromazine or from the class of ecdysone agonists consisting of methoxyfenozide, tebufenozide and azadirachtin; A.10 Mitochondrial electron transport inhibitors selected from pyridaben, tolfenpyrad or flufenerim.

A.11 Voltage-dependent sodium channel blockers selected from indoxacarb or metaflumizone.

A.12 Inhibitors of the lipid synthesis selected from spirodiclofen, spiromesifen or spirotetramat.

A.13 A group of various compounds consisting of amidoflumet, amitraz, bifenazate, clofentezine, cyenopyrafen, cyflumetofen, etoxazole, flonicamid, flubendiamine, flupyrazophos, hexythiazox, piperonyl butoxide, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliprole and the anthranilamid compound II.A^(13.1):

and the sulfoximine compounds II.A^(13.2)

in synergistically effective amounts.

The present invention also provides methods for the control of insects, acarids or nematodes comprising contacting the insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of mixtures of the active compound I with at least one active compound II.

Moreover, the present invention also relates to a method of protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a pesticidally effective amount of a mixture of the active compound I with at least one active compound II.

The invention also provides a method for the protection of seeds from soil insects and of the seedlings' roots and shoots from soil and foliar insects which comprises contacting the seeds before sowing and/or after pregermination with a pesticidally effective amount of a mixture of the active compound I with at least one active compound II.

The invention also relates to the use of a mixture of the active compound I with at least one compound II for combating insects, arachnids or nematodes.

One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.

Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of pests.

There also exists the need for pest control agents that combine know-down activity with prolonged control, that is, fast action with long lasting action.

Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests which have developed natural or adapted resistance against the active compound in question. Therefore there is a need for pest control agents that help prevent or overcome resistance.

It was therefore an object of the present invention to provide pesticidal mixtures which solves at least one of the discussed problems as reducing the dosage rate, enhancing the spectrum of activity or combining know-down activity with prolonged control or as to resistance management.

We have found that this object is in part or in whole achieved by the combination of active compounds defined at the outset. Moreover, we have found that simultaneous, that is joint or separate, application of an active compound I and one or more compounds II or successive application of an active compound I and one or more compounds II allows enhanced control of pests compared to the control rates that are possible with the individual compounds.

Compounds I of the formula I, their preparation and their action against insect and acarid pests have been described generically in WO 2005/63724.

The prior art does not disclose pesticidal mixtures comprising selective aminothiazoline compounds according to the present invention showing unexpected and synergistic effects in combination with other pesticidically active compounds.

The commercially available compounds of the group A may be found in The Pesticide Manual, 13^(th) Edition, British Crop Protection Council (2003) among other publications. Thiamides derivatives in analogy of formula II.A^(2.1) and their preparation have been described in WO 98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p. 237-243 and in U.S. Pat. No. 4,822,779. Pyrafluprole and its preparation have been described in JP-A 2002-193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in U.S. Pat. No. 6,335,357. Amidoflumet and its preparation have been described in U.S. Pat. No. 6,221,890 and in JP-A 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. Cyflumetofen and its preparation have been described in WO 04/080180. Preparation methods for neonicotinoids similar to AKD-1022 have been described by Zhang, A. et al. in J. Neurochemistry, 75(3), 2000. Anthranilamides derivatives in analogy of formula II.A^(13.1) and their preparation have been described in WO 01/70671; WO 02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO 04/33468 and WO 05/118552. Sulfoximine derivatives of and in analogy of formulae II.A^(13.2), II.A^(13.3) or II.A^(13.4) and their preparations have been described in WO 2006/060029.

Preferences Preferred Compounds I of Formula I

With regard to their use in the pesticidal mixtures of the present invention, compounds I of formula I are preferred, wherein

R¹ is hydrogen or COCH₃; R² is selected from fluoro, chloro or CH₃; R³, R⁴ are selected independently from one another from hydrogen, fluoro, chloro, CF₃ or CH₃; R⁵, R⁶ are selected from hydrogen or CH₃, wherein at least one of R⁵ or R⁶ is not hydrogen.

Especially preferred are compounds I of formula I having the following meanings:

R¹ is hydrogen;

R², R³ are CH₃;

R⁴ is hydrogen;

R⁵, R⁶ are CH₃,

or R¹ is hydrogen; R², R³ are chloro; R⁴ is hydrogen;

R⁵, R⁶ are CH₃.

Further preferred are compounds I of formula I having the following meanings:

R¹ is COCH₃; R², R³ are CH₃;

R⁴ is hydrogen;

R⁵, R⁶ are CH₃,

or

R¹ is COCH₃;

R², R³ are chloro; R⁴ is hydrogen;

R⁵, R⁶ are CH₃.

In cases wherein R¹ is hydrogen, active compounds I of formula I can also be represented by the following tautomers of formula I-H^(1a) and I-H^(1b):

Preferred compound I examples of aminothiazoline compounds of formula I are given in the following table C.I:

TABLE C.I: Com- pound I R¹ R² R³ R⁴ R⁵ R⁶ C.I-1 H Cl Cl H H CH₃ C.I-2 H Cl Cl H H Cl C.I-3 H Cl Cl H H CF₃ C.I-4 H Cl Cl H H Br C.I-5 H Cl Cl H H OCH₃ C.I-6 H Cl Cl H H F C.I-7 H Cl Cl H CH₃ CH₃ C.I-8 H Cl Cl H Cl Cl C.I-9 H Cl Cl H CF₃ CF₃ C.I-10 H Cl Cl H OCH₃ OCH₃ C.I-11 H CH₃ CH₃ H H CH₃ C.I-12 H CH₃ CH₃ H H Cl C.I-13 H CH₃ CH₃ H H CF₃ C.I-14 H CH₃ CH₃ H H Br C.I-15 H CH₃ CH₃ H H OCH₃ C.I-16 H CH₃ CH₃ H H F C.I-17 H CH₃ CH₃ H CH₃ CH₃ C.I-18 H CH₃ CH₃ H Cl Cl C.I-19 H CH₃ CH₃ H CF₃ CF₃ C.I-20 H CH₃ CH₃ H OCH₃ OCH₃ C.I-21 H CH₃ CF₃ H H CH₃ C.I-22 H CH₃ CF₃ H H Cl C.I-23 H CH₃ CF₃ H H CF₃ C.I-24 H CH₃ CF₃ H H Br C.I-25 H CH₃ CF₃ H H OCH₃ C.I-26 H CH₃ CF₃ H H F C.I-27 H CH₃ CF₃ H CH₃ CH₃ C.I-28 H CH₃ CF₃ H Cl Cl C.I-29 H CH₃ CF₃ H CF₃ CF₃ C.I-30 H CH₃ CF₃ H OCH₃ OCH₃ C.I-31 H CF₃ CH₃ H H CH₃ C.I-32 H CF₃ CH₃ H H Cl C.I-33 H CF₃ CH₃ H H CF₃ C.I-34 H CF₃ CH₃ H H Br C.I-35 H CF₃ CH₃ H H OCH₃ C.I-36 H CF₃ CH₃ H H F C.I-37 H CF₃ CH₃ H CH₃ CH₃ C.I-38 H CF₃ CH₃ H Cl Cl C.I-39 H CF₃ CH₃ H CF₃ CF₃ C.I-40 H CF₃ CH₃ H OCH₃ OCH₃ C.I-41 H F CF₃ H H CH₃ C.I-42 H F CF₃ H H Cl C.I-43 H F CF₃ H H CF₃ C.I-44 H F CF₃ H H Br C.I-45 H F CF₃ H H OCH₃ C.I-46 H F CF₃ H H F C.I-47 H F CF₃ H CH₃ CH₃ C.I-48 H F CF₃ H Cl Cl C.I-49 H F CF₃ H CF₃ CF₃ C.I-50 H F CF₃ H OCH₃ OCH₃ C.I-51 H Cl CF₃ H H CH₃ C.I-52 H Cl CF₃ H H Cl C.I-53 H Cl CF₃ H H CF₃ C.I-54 H Cl CF₃ H H Br C.I-55 H Cl CF₃ H H OCH₃ C.I-56 H Cl CF₃ H H F C.I-57 H Cl CF₃ H CH₃ CH₃ C.I-58 H Cl CF₃ H Cl Cl C.I-59 H Cl CF₃ H CF₃ CF₃ C.I-60 H Cl CF₃ H OCH₃ OCH₃ C.I-61 H CH₃ Cl H H CH₃ C.I-62 H CH₃ Cl H H Cl C.I-63 H CH₃ Cl H H CF₃ C.I-64 H CH₃ Cl H H Br C.I-65 H CH₃ Cl H H OCH₃ C.I-66 H CH₃ Cl H H F C.I-67 H CH₃ Cl H CH₃ CH₃ C.I-68 H CH₃ Cl H Cl Cl C.I-69 H CH₃ Cl H CF₃ CF₃ C.I-70 H CH₃ Cl H OCH₃ OCH₃ C.I-71 H Cl CH₃ H H CH₃ C.I-72 H Cl CH₃ H H Cl C.I-73 H Cl CH₃ H H CF₃ C.I-74 H Cl CH₃ H H Br C.I-75 H Cl CH₃ H H OCH₃ C.I-76 H Cl CH₃ H H F C.I-77 H Cl CH₃ H CH₃ CH₃ C.I-78 H Cl CH₃ H Cl Cl C.I-79 H Cl CH₃ H CF₃ CF₃ C.I-80 H Cl CH₃ H OCH₃ OCH₃ C.I-81 H Cl H Cl H CH₃ C.I-82 H Cl H Cl H Cl C.I-83 H Cl H Cl H CF₃ C.I-84 H Cl H Cl H Br C.I-85 H Cl H Cl H OCH₃ C.I-86 H Cl H Cl H F C.I-87 H Cl H Cl CH₃ CH₃ C.I-88 H Cl H Cl Cl Cl C.I-89 H Cl H Cl CF₃ CF₃ C.I-90 H Cl H Cl OCH₃ OCH₃ C.I-91 H F H F H CH₃ C.I-92 H F H F H Cl C.I-93 H F H F H CF₃ C.I-94 H F H F H Br C.I-95 H F H F H OCH₃ C.I-96 H F H F H F C.I-97 H F H F CH₃ CH₃ C.I-98 H F H F Cl Cl C.I-99 H F H F CF₃ CF₃ C.I-100 H F H F OCH₃ OCH₃ C.I-101 H CH₃ H CH₃ H CH₃ C.I-102 H CH₃ H CH₃ H Cl C.I-103 H CH₃ H CH₃ H CF₃ C.I-104 H CH₃ H CH₃ H Br C.I-105 H CH₃ H CH₃ H OCH₃ C.I-106 H CH₃ H CH₃ H F C.I-107 H CH₃ H CH₃ CH₃ CH₃ C.I-108 H CH₃ H CH₃ Cl Cl C.I-109 H CH₃ H CH₃ CF₃ CF₃ C.I-110 H CH₃ H CH₃ OCH₃ OCH₃ C.I-111 H F H CH₃ H CH₃ C.I-112 H F H CH₃ H Cl C.I-113 H F H CH₃ H CF₃ C.I-114 H F H CH₃ H Br C.I-115 H F H CH₃ H OCH₃ C.I-116 H F H CH₃ H F C.I-117 H F H CH₃ CH₃ CH₃ C.I-118 H F H CH₃ Cl Cl C.I-119 H F H CH₃ CF₃ CF₃ C.I-120 H F H CH₃ OCH₃ OCH₃ C.I-121 H F H CF₃ H CH₃ C.I-122 H F H CF₃ H Cl C.I-123 H F H CF₃ H CF₃ C.I-124 H F H CF₃ H Br C.I-125 H F H CF₃ H OCH₃ C.I-126 H F H CF₃ H F C.I-127 H F H CF₃ CH₃ CH₃ C.I-128 H F H CF₃ Cl Cl C.I-129 H F H CF₃ CF₃ CF₃ C.I-130 H F H CF₃ OCH₃ OCH₃ C.I-131 H F H OCH₃ H CH₃ C.I-132 H F H OCH₃ H Cl C.I-133 H F H OCH₃ H CF₃ C.I-134 H F H OCH₃ H Br C.I-135 H F H OCH₃ H OCH₃ C.I-136 H F H OCH₃ H F C.I-137 H F H OCH₃ CH₃ CH₃ C.I-138 H F H OCH₃ Cl Cl C.I-139 H F H OCH₃ CF₃ CF₃ C.I-140 H F H OCH₃ OCH₃ OCH₃ C.I-141 H F H Br H CH₃ C.I-142 H F H Br H Cl C.I-143 H F H Br H CF₃ C.I-144 H F H Br H Br C.I-145 H F H Br H OCH₃ C.I-146 H F H Br H F C.I-147 H F H Br CH₃ CH₃ C.I-148 H F H Br Cl Cl C.I-149 H F H Br CF₃ CF₃ C.I-150 H F H Br OCH₃ OCH₃ C.I-151 H Br H F H CH₃ C.I-152 H Br H F H Cl C.I-153 H Br H F H CF₃ C.I-154 H Br H F H Br C.I-155 H Br H F H OCH₃ C.I-156 H Br H F H F C.I-157 H Br H F CH₃ CH₃ C.I-158 H Br H F Cl Cl C.I-159 H Br H F CF₃ CF₃ C.I-160 H Br H F OCH₃ OCH₃ C.I-161 H CH₃ H F H CH₃ C.I-162 H CH₃ H F H Cl C.I-163 H CH₃ H F H CF₃ C.I-164 H CH₃ H F H Br C.I-165 H CH₃ H F H OCH₃ C.I-166 H CH₃ H F H F C.I-167 H CH₃ H F CH₃ CH₃ C.I-168 H CH₃ H F Cl Cl C.I-169 H CH₃ H F CF₃ CF₃ C.I-170 H CH₃ H F OCH₃ OCH₃ C.I-171 H OCH₃ H F H CH₃ C.I-172 H OCH₃ H F H Cl C.I-173 H OCH₃ H F H CF₃ C.I-174 H OCH₃ H F H Br C.I-175 H OCH₃ H F H OCH₃ C.I-176 H OCH₃ H F H F C.I-177 H OCH₃ H F CH₃ CH₃ C.I-178 H OCH₃ H F Cl Cl C.I-179 H OCH₃ H F CF₃ CF₃ C.I-180 H OCH₃ H F OCH₃ OCH₃ C.I-181 H CH₃ H Cl H CH₃ C.I-182 H CH₃ H Cl H Cl C.I-183 H CH₃ H Cl H CF₃ C.I-184 H CH₃ H Cl H Br C.I-185 H CH₃ H Cl H OCH₃ C.I-186 H CH₃ H Cl H F C.I-187 H CH₃ H Cl CH₃ CH₃ C.I-188 H CH₃ H Cl Cl Cl C.I-189 H CH₃ H Cl CF₃ CF₃ C.I-190 H CH₃ H Cl OCH₃ OCH₃ C.I-191 H Cl H CH₃ H CH₃ C.I-192 H Cl H CH₃ H Cl C.I-193 H Cl H CH₃ H CF₃ C.I-194 H Cl H CH₃ H Br C.I-195 H Cl H CH₃ H OCH₃ C.I-196 H Cl H CH₃ H F C.I-197 H Cl H CH₃ CH₃ CH₃ C.I-198 H Cl H CH₃ Cl Cl C.I-199 H Cl H CH₃ CF₃ CF₃ C.I-200 H Cl H CH₃ OCH₃ OCH₃ C.I-201 COCH₃ Cl Cl H H CH₃ C.I-202 COCH₃ Cl Cl H H Cl C.I-203 COCH₃ Cl Cl H H CF₃ C.I-204 COCH₃ Cl Cl H H Br C.I-205 COCH₃ Cl Cl H H OCH₃ C.I-206 COCH₃ Cl Cl H H F C.I-207 COCH₃ Cl Cl H CH₃ CH₃ C.I-208 COCH₃ Cl Cl H Cl Cl C.I-209 COCH₃ Cl Cl H CF₃ CF₃ C.I-210 COCH₃ Cl Cl H OCH₃ OCH₃ C.I-211 COCH₃ CH₃ CH₃ H H CH₃ C.I-212 COCH₃ CH₃ CH₃ H H Cl C.I-213 COCH₃ CH₃ CH₃ H H CF₃ C.I-214 COCH₃ CH₃ CH₃ H H Br C.I-215 COCH₃ CH₃ CH₃ H H OCH₃ C.I-216 COCH₃ CH₃ CH₃ H H F C.I-217 COCH₃ CH₃ CH₃ H CH₃ CH₃ C.I-218 COCH₃ CH₃ CH₃ H Cl Cl C.I-219 COCH₃ CH₃ CH₃ H CF₃ CF₃ C.I-220 COCH₃ CH₃ CH₃ H OCH₃ OCH₃ C.I-221 COCH₃ CH₃ CF₃ H H CH₃ C.I-222 COCH₃ CH₃ CF₃ H H Cl C.I-223 COCH₃ CH₃ CF₃ H H CF₃ C.I-224 COCH₃ CH₃ CF₃ H H Br C.I-225 COCH₃ CH₃ CF₃ H H OCH₃ C.I-226 COCH₃ CH₃ CF₃ H H F C.I-227 COCH₃ CH₃ CF₃ H CH₃ CH₃ C.I-228 COCH₃ CH₃ CF₃ H Cl Cl C.I-229 COCH₃ CH₃ CF₃ H CF₃ CF₃ C.I-230 COCH₃ CH₃ CF₃ H OCH₃ OCH₃ C.I-231 COCH₃ CF₃ CH₃ H H CH₃ C.I-232 COCH₃ CF₃ CH₃ H H Cl C.I-233 COCH₃ CF₃ CH₃ H H CF₃ C.I-234 COCH₃ CF₃ CH₃ H H Br C.I-235 COCH₃ CF₃ CH₃ H H OCH₃ C.I-236 COCH₃ CF₃ CH₃ H H F C.I-237 COCH₃ CF₃ CH₃ H CH₃ CH₃ C.I-238 COCH₃ CF₃ CH₃ H Cl Cl C.I-239 COCH₃ CF₃ CH₃ H CF₃ CF₃ C.I-240 COCH₃ CF₃ CH₃ H OCH₃ OCH₃ C.I-241 COCH₃ F CF₃ H H CH₃ C.I-242 COCH₃ F CF₃ H H Cl C.I-243 COCH₃ F CF₃ H H CF₃ C.I-244 COCH₃ F CF₃ H H Br C.I-245 COCH₃ F CF₃ H H OCH₃ C.I-246 COCH₃ F CF₃ H H F C.I-247 COCH₃ F CF₃ H CH₃ CH₃ C.I-248 COCH₃ F CF₃ H Cl Cl C.I-249 COCH₃ F CF₃ H CF₃ CF₃ C.I-250 COCH₃ F CF₃ H OCH₃ OCH₃ C.I-251 COCH₃ Cl CF₃ H H CH₃ C.I-252 COCH₃ Cl CF₃ H H Cl C.I-253 COCH₃ Cl CF₃ H H CF₃ C.I-254 COCH₃ Cl CF₃ H H Br C.I-255 COCH₃ Cl CF₃ H H OCH₃ C.I-256 COCH₃ Cl CF₃ H H F C.I-257 COCH₃ Cl CF₃ H CH₃ CH₃ C.I-258 COCH₃ Cl CF₃ H Cl Cl C.I-259 COCH₃ Cl CF₃ H CF₃ CF₃ C.I-260 COCH₃ Cl CF₃ H OCH₃ OCH₃ C.I-261 COCH₃ CH₃ Cl H H CH₃ C.I-262 COCH₃ CH₃ Cl H H Cl C.I-263 COCH₃ CH₃ Cl H H CF₃ C.I-264 COCH₃ CH₃ Cl H H Br C.I-265 COCH₃ CH₃ Cl H H OCH₃ C.I-266 COCH₃ CH₃ Cl H H F C.I-267 COCH₃ CH₃ Cl H CH₃ CH₃ C.I-268 COCH₃ CH₃ Cl H Cl Cl C.I-269 COCH₃ CH₃ Cl H CF₃ CF₃ C.I-270 COCH₃ CH₃ Cl H OCH₃ OCH₃ C.I-271 COCH₃ Cl CH₃ H H CH₃ C.I-272 COCH₃ Cl CH₃ H H Cl C.I-273 COCH₃ Cl CH₃ H H CF₃ C.I-274 COCH₃ Cl CH₃ H H Br C.I-275 COCH₃ Cl CH₃ H H OCH₃ C.I-276 COCH₃ Cl CH₃ H H F C.I-277 COCH₃ Cl CH₃ H CH₃ CH₃ C.I-278 COCH₃ Cl CH₃ H Cl Cl C.I-279 COCH₃ Cl CH₃ H CF₃ CF₃ C.I-280 COCH₃ Cl CH₃ H OCH₃ OCH₃ C.I-281 COCH₃ Cl H Cl H CH₃ C.I-282 COCH₃ Cl H Cl H Cl C.I-283 COCH₃ Cl H Cl H CF₃ C.I-284 COCH₃ Cl H Cl H Br C.I-285 COCH₃ Cl H Cl H OCH₃ C.I-286 COCH₃ Cl H Cl H F C.I-287 COCH₃ Cl H Cl CH₃ CH₃ C.I-288 COCH₃ Cl H Cl Cl Cl C.I-289 COCH₃ Cl H Cl CF₃ CF₃ C.I-290 COCH₃ Cl H Cl OCH₃ OCH₃ C.I-291 COCH₃ F H F H CH₃ C.I-292 COCH₃ F H F H Cl C.I-293 COCH₃ F H F H CF₃ C.I-294 COCH₃ F H F H Br C.I-295 COCH₃ F H F H OCH₃ C.I-296 COCH₃ F H F H F C.I-297 COCH₃ F H F CH₃ CH₃ C.I-298 COCH₃ F H F Cl Cl C.I-299 COCH₃ F H F CF₃ CF₃ C.I-300 COCH₃ F H F OCH₃ OCH₃ C.I-301 COCH₃ CH₃ H CH₃ H CH₃ C.I-302 COCH₃ CH₃ H CH₃ H Cl C.I-303 COCH₃ CH₃ H CH₃ H CF₃ C.I-304 COCH₃ CH₃ H CH₃ H Br C.I-305 COCH₃ CH₃ H CH₃ H OCH₃ C.I-306 COCH₃ CH₃ H CH₃ H F C.I-307 COCH₃ CH₃ H CH₃ CH₃ CH₃ C.I-308 COCH₃ CH₃ H CH₃ Cl Cl C.I-309 COCH₃ CH₃ H CH₃ CF₃ CF₃ C.I-310 COCH₃ CH₃ H CH₃ OCH₃ OCH₃ C.I-311 COCH₃ F H CH₃ H CH₃ C.I-312 COCH₃ F H CH₃ H Cl C.I-313 COCH₃ F H CH₃ H CF₃ C.I-314 COCH₃ F H CH₃ H Br C.I-315 COCH₃ F H CH₃ H OCH₃ C.I-316 COCH₃ F H CH₃ H F C.I-317 COCH₃ F H CH₃ CH₃ CH₃ C.I-318 COCH₃ F H CH₃ Cl Cl C.I-319 COCH₃ F H CH₃ CF₃ CF₃ C.I-320 COCH₃ F H CH₃ OCH₃ OCH₃ C.I-321 COCH₃ F H CF₃ H CH₃ C.I-322 COCH₃ F H CF₃ H Cl C.I-323 COCH₃ F H CF₃ H CF₃ C.I-324 COCH₃ F H CF₃ H Br C.I-325 COCH₃ F H CF₃ H OCH₃ C.I-326 COCH₃ F H CF₃ H F C.I-327 COCH₃ F H CF₃ CH₃ CH₃ C.I-328 COCH₃ F H CF₃ Cl Cl C.I-329 COCH₃ F H CF₃ CF₃ CF₃ C.I-330 COCH₃ F H CF₃ OCH₃ OCH₃ C.I-331 COCH₃ F H OCH₃ H CH₃ C.I-332 COCH₃ F H OCH₃ H Cl C.I-333 COCH₃ F H OCH₃ H CF₃ C.I-334 COCH₃ F H OCH₃ H Br C.I-335 COCH₃ F H OCH₃ H OCH₃ C.I-336 COCH₃ F H OCH₃ H F C.I-337 COCH₃ F H OCH₃ CH₃ CH₃ C.I-338 COCH₃ F H OCH₃ Cl Cl C.I-339 COCH₃ F H OCH₃ CF₃ CF₃ C.I-340 COCH₃ F H OCH₃ OCH₃ OCH₃ C.I-341 COCH₃ F H Br H CH₃ C.I-342 COCH₃ F H Br H Cl C.I-343 COCH₃ F H Br H CF₃ C.I-344 COCH₃ F H Br H Br C.I-345 COCH₃ F H Br H OCH₃ C.I-346 COCH₃ F H Br H F C.I-347 COCH₃ F H Br CH₃ CH₃ C.I-348 COCH₃ F H Br Cl Cl C.I-349 COCH₃ F H Br CF₃ CF₃ C.I-350 COCH₃ F H Br OCH₃ OCH₃ C.I-351 COCH₃ Br H F H CH₃ C.I-352 COCH₃ Br H F H Cl C.I-353 COCH₃ Br H F H CF₃ C.I-354 COCH₃ Br H F H Br C.I-355 COCH₃ Br H F H OCH₃ C.I-356 COCH₃ Br H F H F C.I-357 COCH₃ Br H F CH₃ CH₃ C.I-358 COCH₃ Br H F Cl Cl C.I-359 COCH₃ Br H F CF₃ CF₃ C.I-360 COCH₃ Br H F OCH₃ OCH₃ C.I-361 COCH₃ CH₃ H F H CH₃ C.I-362 COCH₃ CH₃ H F H Cl C.I-363 COCH₃ CH₃ H F H CF₃ C.I-364 COCH₃ CH₃ H F H Br C.I-365 COCH₃ CH₃ H F H OCH₃ C.I-366 COCH₃ CH₃ H F H F C.I-367 COCH₃ CH₃ H F CH₃ CH₃ C.I-368 COCH₃ CH₃ H F Cl Cl C.I-369 COCH₃ CH₃ H F CF₃ CF₃ C.I-370 COCH₃ CH₃ H F OCH₃ OCH₃ C.I-371 COCH₃ OCH₃ H F H CH₃ C.I-372 COCH₃ OCH₃ H F H Cl C.I-373 COCH₃ OCH₃ H F H CF₃ C.I-374 COCH₃ OCH₃ H F H Br C.I-375 COCH₃ OCH₃ H F H OCH₃ C.I-376 COCH₃ OCH₃ H F H F C.I-377 COCH₃ OCH₃ H F CH₃ CH₃ C.I-378 COCH₃ OCH₃ H F Cl Cl C.I-379 COCH₃ OCH₃ H F CF₃ CF₃ C.I-380 COCH₃ OCH₃ H F OCH₃ OCH₃ C.I-381 COCH₃ CH₃ H Cl H CH₃ C.I-382 COCH₃ CH₃ H Cl H Cl C.I-383 COCH₃ CH₃ H Cl H CF₃ C.I-384 COCH₃ CH₃ H Cl H Br C.I-385 COCH₃ CH₃ H Cl H OCH₃ C.I-386 COCH₃ CH₃ H Cl H F C.I-387 COCH₃ CH₃ H Cl CH₃ CH₃ C.I-388 COCH₃ CH₃ H Cl Cl Cl C.I-389 COCH₃ CH₃ H Cl CF₃ CF₃ C.I-390 COCH₃ CH₃ H Cl OCH₃ OCH₃ C.I-391 COCH₃ Cl H CH₃ H CH₃ C.I-392 COCH₃ Cl H CH₃ H Cl C.I-393 COCH₃ Cl H CH₃ H CF₃ C.I-394 COCH₃ Cl H CH₃ H Br C.I-395 COCH₃ Cl H CH₃ H OCH₃ C.I-396 COCH₃ Cl H CH₃ H F C.I-397 COCH₃ Cl H CH₃ CH₃ CH₃ C.I-398 COCH₃ Cl H CH₃ Cl Cl C.I-399 COCH₃ Cl H CH₃ CF₃ CF₃ C.I-400 COCH₃ Cl H CH₃ OCH₃ OCH₃ C.I-401 COCH₂OCH₃ Cl Cl H H CH₃ C.I-402 COCH₂OCH₃ Cl Cl H H Cl C.I-403 COCH₂OCH₃ Cl Cl H H CF₃ C.I-404 COCH₂OCH₃ Cl Cl H H Br C.I-405 COCH₂OCH₃ Cl Cl H H OCH₃ C.I-406 COCH₂OCH₃ Cl Cl H H F C.I-407 COCH₂OCH₃ Cl Cl H CH₃ CH₃ C.I-408 COCH₂OCH₃ Cl Cl H Cl Cl C.I-409 COCH₂OCH₃ Cl Cl H CF₃ CF₃ C.I-410 COCH₂OCH₃ Cl Cl H OCH₃ OCH₃ C.I-411 COCH₂OCH₃ CH₃ CH₃ H H CH₃ C.I-412 COCH₂OCH₃ CH₃ CH₃ H H Cl C.I-413 COCH₂OCH₃ CH₃ CH₃ H H CF₃ C.I-414 COCH₂OCH₃ CH₃ CH₃ H H Br C.I-415 COCH₂OCH₃ CH₃ CH₃ H H OCH₃ C.I-416 COCH₂OCH₃ CH₃ CH₃ H H F C.I-417 COCH₂OCH₃ CH₃ CH₃ H CH₃ CH₃ C.I-418 COCH₂OCH₃ CH₃ CH₃ H Cl Cl C.I-419 COCH₂OCH₃ CH₃ CH₃ H CF₃ CF₃ C.I-420 COCH₂OCH₃ CH₃ CH₃ H OCH₃ OCH₃ C.I-421 COCH₂OCH₃ CH₃ CF₃ H H CH₃ C.I-422 COCH₂OCH₃ CH₃ CF₃ H H Cl C.I-423 COCH₂OCH₃ CH₃ CF₃ H H CF₃ C.I-424 COCH₂OCH₃ CH₃ CF₃ H H Br C.I-425 COCH₂OCH₃ CH₃ CF₃ H H OCH₃ C.I-426 COCH₂OCH₃ CH₃ CF₃ H H F C.I-427 COCH₂OCH₃ CH₃ CF₃ H CH₃ CH₃ C.I-428 COCH₂OCH₃ CH₃ CF₃ H Cl Cl C.I-429 COCH₂OCH₃ CH₃ CF₃ H CF₃ CF₃ C.I-430 COCH₂OCH₃ CH₃ CF₃ H OCH₃ OCH₃ C.I-431 COCH₂OCH₃ CF₃ CH₃ H H CH₃ C.I-432 COCH₂OCH₃ CF₃ CH₃ H H Cl C.I-433 COCH₂OCH₃ CF₃ CH₃ H H CF₃ C.I-434 COCH₂OCH₃ CF₃ CH₃ H H Br C.I-435 COCH₂OCH₃ CF₃ CH₃ H H OCH₃ C.I-436 COCH₂OCH₃ CF₃ CH₃ H H F C.I-437 COCH₂OCH₃ CF₃ CH₃ H CH₃ CH₃ C.I-438 COCH₂OCH₃ CF₃ CH₃ H Cl Cl C.I-439 COCH₂OCH₃ CF₃ CH₃ H CF₃ CF₃ C.I-440 COCH₂OCH₃ CF₃ CH₃ H OCH₃ OCH₃ C.I-441 COCH₂OCH₃ F CF₃ H H CH₃ C.I-442 COCH₂OCH₃ F CF₃ H H Cl C.I-443 COCH₂OCH₃ F CF₃ H H CF₃ C.I-444 COCH₂OCH₃ F CF₃ H H Br C.I-445 COCH₂OCH₃ F CF₃ H H OCH₃ C.I-446 COCH₂OCH₃ F CF₃ H H F C.I-447 COCH₂OCH₃ F CF₃ H CH₃ CH₃ C.I-448 COCH₂OCH₃ F CF₃ H Cl Cl C.I-449 COCH₂OCH₃ F CF₃ H CF₃ CF₃ C.I-450 COCH₂OCH₃ F CF₃ H OCH₃ OCH₃ C.I-451 COCH₂OCH₃ Cl CF₃ H H CH₃ C.I-452 COCH₂OCH₃ Cl CF₃ H H Cl C.I-453 COCH₂OCH₃ Cl CF₃ H H CF₃ C.I-454 COCH₂OCH₃ Cl CF₃ H H Br C.I-455 COCH₂OCH₃ Cl CF₃ H H OCH₃ C.I-456 COCH₂OCH₃ Cl CF₃ H H F C.I-457 COCH₂OCH₃ Cl CF₃ H CH₃ CH₃ C.I-458 COCH₂OCH₃ Cl CF₃ H Cl Cl C.I-459 COCH₂OCH₃ Cl CF₃ H CF₃ CF₃ C.I-460 COCH₂OCH₃ Cl CF₃ H OCH₃ OCH₃ C.I-461 COCH₂OCH₃ CH₃ Cl H H CH₃ C.I-462 COCH₂OCH₃ CH₃ Cl H H Cl C.I-463 COCH₂OCH₃ CH₃ Cl H H CF₃ C.I-464 COCH₂OCH₃ CH₃ Cl H H Br C.I-465 COCH₂OCH₃ CH₃ Cl H H OCH₃ C.I-466 COCH₂OCH₃ CH₃ Cl H H F C.I-467 COCH₂OCH₃ CH₃ Cl H CH₃ CH₃ C.I-468 COCH₂OCH₃ CH₃ Cl H Cl Cl C.I-469 COCH₂OCH₃ CH₃ Cl H CF₃ CF₃ C.I-470 COCH₂OCH₃ CH₃ Cl H OCH₃ OCH₃ C.I-471 COCH₂OCH₃ Cl CH₃ H H CH₃ C.I-472 COCH₂OCH₃ Cl CH₃ H H Cl C.I-473 COCH₂OCH₃ Cl CH₃ H H CF₃ C.I-474 COCH₂OCH₃ Cl CH₃ H H Br C.I-475 COCH₂OCH₃ Cl CH₃ H H OCH₃ C.I-476 COCH₂OCH₃ Cl CH₃ H H F C.I-477 COCH₂OCH₃ Cl CH₃ H CH₃ CH₃ C.I-478 COCH₂OCH₃ Cl CH₃ H Cl Cl C.I-479 COCH₂OCH₃ Cl CH₃ H CF₃ CF₃ C.I-480 COCH₂OCH₃ Cl CH₃ H OCH₃ OCH₃ C.I-481 COCH₂OCH₃ Cl H Cl H CH₃ C.I-482 COCH₂OCH₃ Cl H Cl H Cl C.I-483 COCH₂OCH₃ Cl H Cl H CF₃ C.I-484 COCH₂OCH₃ Cl H Cl H Br C.I-485 COCH₂OCH₃ Cl H Cl H OCH₃ C.I-486 COCH₂OCH₃ Cl H Cl H F C.I-487 COCH₂OCH₃ Cl H Cl CH₃ CH₃ C.I-488 COCH₂OCH₃ Cl H Cl Cl Cl C.I-489 COCH₂OCH₃ Cl H Cl CF₃ CF₃ C.I-490 COCH₂OCH₃ Cl H Cl OCH₃ OCH₃ C.I-491 COCH₂OCH₃ F H F H CH₃ C.I-492 COCH₂OCH₃ F H F H Cl C.I-493 COCH₂OCH₃ F H F H CF₃ C.I-494 COCH₂OCH₃ F H F H Br C.I-495 COCH₂OCH₃ F H F H OCH₃ C.I-496 COCH₂OCH₃ F H F H F C.I-497 COCH₂OCH₃ F H F CH₃ CH₃ C.I-498 COCH₂OCH₃ F H F Cl Cl C.I-499 COCH₂OCH₃ F H F CF₃ CF₃ C.I-500 COCH₂OCH₃ F H F OCH₃ OCH₃ C.I-501 COCH₂OCH₃ CH₃ H CH₃ H CH₃ C.I-502 COCH₂OCH₃ CH₃ H CH₃ H Cl C.I-503 COCH₂OCH₃ CH₃ H CH₃ H CF₃ C.I-504 COCH₂OCH₃ CH₃ H CH₃ H Br C.I-505 COCH₂OCH₃ CH₃ H CH₃ H OCH₃ C.I-506 COCH₂OCH₃ CH₃ H CH₃ H F C.I-507 COCH₂OCH₃ CH₃ H CH₃ CH₃ CH₃ C.I-508 COCH₂OCH₃ CH₃ H CH₃ Cl Cl C.I-509 COCH₂OCH₃ CH₃ H CH₃ CF₃ CF₃ C.I-510 COCH₂OCH₃ CH₃ H CH₃ OCH₃ OCH₃ C.I-511 COCH₂OCH₃ F H CH₃ H CH₃ C.I-512 COCH₂OCH₃ F H CH₃ H Cl C.I-513 COCH₂OCH₃ F H CH₃ H CF₃ C.I-514 COCH₂OCH₃ F H CH₃ H Br C.I-515 COCH₂OCH₃ F H CH₃ H OCH₃ C.I-516 COCH₂OCH₃ F H CH₃ H F C.I-517 COCH₂OCH₃ F H CH₃ CH₃ CH₃ C.I-518 COCH₂OCH₃ F H CH₃ Cl Cl C.I-519 COCH₂OCH₃ F H CH₃ CF₃ CF₃ C.I-520 COCH₂OCH₃ F H CH₃ OCH₃ OCH₃ C.I-521 COCH₂OCH₃ F H CF₃ H CH₃ C.I-522 COCH₂OCH₃ F H CF₃ H Cl C.I-523 COCH₂OCH₃ F H CF₃ H CF₃ C.I-524 COCH₂OCH₃ F H CF₃ H Br C.I-525 COCH₂OCH₃ F H CF₃ H OCH₃ C.I-526 COCH₂OCH₃ F H CF₃ H F C.I-527 COCH₂OCH₃ F H CF₃ CH₃ CH₃ C.I-528 COCH₂OCH₃ F H CF₃ Cl Cl C.I-529 COCH₂OCH₃ F H CF₃ CF₃ CF₃ C.I-530 COCH₂OCH₃ F H CF₃ OCH₃ OCH₃ C.I-531 COCH₂OCH₃ F H OCH₃ H CH₃ C.I-532 COCH₂OCH₃ F H OCH₃ H Cl C.I-533 COCH₂OCH₃ F H OCH₃ H CF₃ C.I-534 COCH₂OCH₃ F H OCH₃ H Br C.I-535 COCH₂OCH₃ F H OCH₃ H OCH₃ C.I-536 COCH₂OCH₃ F H OCH₃ H F C.I-537 COCH₂OCH₃ F H OCH₃ CH₃ CH₃ C.I-538 COCH₂OCH₃ F H OCH₃ Cl Cl C.I-539 COCH₂OCH₃ F H OCH₃ CF₃ CF₃ C.I-540 COCH₂OCH₃ F H OCH₃ OCH₃ OCH₃ C.I-541 COCH₂OCH₃ F H Br H CH₃ C.I-542 COCH₂OCH₃ F H Br H Cl C.I-543 COCH₂OCH₃ F H Br H CF₃ C.I-544 COCH₂OCH₃ F H Br H Br C.I-545 COCH₂OCH₃ F H Br H OCH₃ C.I-546 COCH₂OCH₃ F H Br H F C.I-547 COCH₂OCH₃ F H Br CH₃ CH₃ C.I-548 COCH₂OCH₃ F H Br Cl Cl C.I-549 COCH₂OCH₃ F H Br CF₃ CF₃ C.I-550 COCH₂OCH₃ F H Br OCH₃ OCH₃ C.I-551 COCH₂OCH₃ Br H F H CH₃ C.I-552 COCH₂OCH₃ Br H F H Cl C.I-553 COCH₂OCH₃ Br H F H CF₃ C.I-554 COCH₂OCH₃ Br H F H Br C.I-555 COCH₂OCH₃ Br H F H OCH₃ C.I-556 COCH₂OCH₃ Br H F H F C.I-557 COCH₂OCH₃ Br H F CH₃ CH₃ C.I-558 COCH₂OCH₃ Br H F Cl Cl C.I-559 COCH₂OCH₃ Br H F CF₃ CF₃ C.I-560 COCH₂OCH₃ Br H F OCH₃ OCH₃ C.I-561 COCH₂OCH₃ CH₃ H F H CH₃ C.I-562 COCH₂OCH₃ CH₃ H F H Cl C.I-563 COCH₂OCH₃ CH₃ H F H CF₃ C.I-564 COCH₂OCH₃ CH₃ H F H Br C.I-565 COCH₂OCH₃ CH₃ H F H OCH₃ C.I-566 COCH₂OCH₃ CH₃ H F H F C.I-567 COCH₂OCH₃ CH₃ H F CH₃ CH₃ C.I-568 COCH₂OCH₃ CH₃ H F Cl Cl C.I-569 COCH₂OCH₃ CH₃ H F CF₃ CF₃ C.I-570 COCH₂OCH₃ CH₃ H F OCH₃ OCH₃ C.I-571 COCH₂OCH₃ OCH₃ H F H CH₃ C.I-572 COCH₂OCH₃ OCH₃ H F H Cl C.I-573 COCH₂OCH₃ OCH₃ H F H CF₃ C.I-574 COCH₂OCH₃ OCH₃ H F H Br C.I-575 COCH₂OCH₃ OCH₃ H F H OCH₃ C.I-576 COCH₂OCH₃ OCH₃ H F H F C.I-577 COCH₂OCH₃ OCH₃ H F CH₃ CH₃ C.I-578 COCH₂OCH₃ OCH₃ H F Cl Cl C.I-579 COCH₂OCH₃ OCH₃ H F CF₃ CF₃ C.I-580 COCH₂OCH₃ OCH₃ H F OCH₃ OCH₃ C.I-581 COCH₂OCH₃ CH₃ H Cl H CH₃ C.I-582 COCH₂OCH₃ CH₃ H Cl H Cl C.I-583 COCH₂OCH₃ CH₃ H Cl H CF₃ C.I-584 COCH₂OCH₃ CH₃ H Cl H Br C.I-585 COCH₂OCH₃ CH₃ H Cl H OCH₃ C.I-586 COCH₂OCH₃ CH₃ H Cl H F C.I-587 COCH₂OCH₃ CH₃ H Cl CH₃ CH₃ C.I-588 COCH₂OCH₃ CH₃ H Cl Cl Cl C.I-589 COCH₂OCH₃ CH₃ H Cl CF₃ CF₃ C.I-590 COCH₂OCH₃ CH₃ H Cl OCH₃ OCH₃ C.I-591 COCH₂OCH₃ Cl H CH₃ H CH₃ C.I-592 COCH₂OCH₃ Cl H CH₃ H Cl C.I-593 COCH₂OCH₃ Cl H CH₃ H CF₃ C.I-594 COCH₂OCH₃ Cl H CH₃ H Br C.I-595 COCH₂OCH₃ Cl H CH₃ H OCH₃ C.I-596 COCH₂OCH₃ Cl H CH₃ H F C.I-597 COCH₂OCH₃ Cl H CH₃ CH₃ CH₃ C.I-598 COCH₂OCH₃ Cl H CH₃ Cl Cl C.I-599 COCH₂OCH₃ Cl H CH₃ CF₃ CF₃ C.I-600 COCH₂OCH₃ Cl H CH₃ OCH₃ OCH₃ C.I-601 COCH₂CH₃ Cl Cl H H CH₃ C.I-602 COCH₂CH₃ Cl Cl H H Cl C.I-603 COCH₂CH₃ Cl Cl H H CF₃ C.I-604 COCH₂CH₃ Cl Cl H H Br C.I-605 COCH₂CH₃ Cl Cl H H OCH₃ C.I-606 COCH₂CH₃ Cl Cl H H F C.I-607 COCH₂CH₃ Cl Cl H CH₃ CH₃ C.I-608 COCH₂CH₃ Cl Cl H Cl Cl C.I-609 COCH₂CH₃ Cl Cl H CF₃ CF₃ C.I-610 COCH₂CH₃ Cl Cl H OCH₃ OCH₃ C.I-611 COCH₂CH₃ CH₃ CH₃ H H CH₃ C.I-612 COCH₂CH₃ CH₃ CH₃ H H Cl C.I-613 COCH₂CH₃ CH₃ CH₃ H H CF₃ C.I-614 COCH₂CH₃ CH₃ CH₃ H H Br C.I-615 COCH₂CH₃ CH₃ CH₃ H H OCH₃ C.I-616 COCH₂CH₃ CH₃ CH₃ H H F C.I-617 COCH₂CH₃ CH₃ CH₃ H CH₃ CH₃ C.I-618 COCH₂CH₃ CH₃ CH₃ H Cl Cl C.I-619 COCH₂CH₃ CH₃ CH₃ H CF₃ CF₃ C.I-620 COCH₂CH₃ CH₃ CH₃ H OCH₃ OCH₃ C.I-621 COCH₂CH₃ CH₃ CF₃ H H CH₃ C.I-622 COCH₂CH₃ CH₃ CF₃ H H Cl C.I-623 COCH₂CH₃ CH₃ CF₃ H H CF₃ C.I-624 COCH₂CH₃ CH₃ CF₃ H H Br C.I-625 COCH₂CH₃ CH₃ CF₃ H H OCH₃ C.I-626 COCH₂CH₃ CH₃ CF₃ H H F C.I-627 COCH₂CH₃ CH₃ CF₃ H CH₃ CH₃ C.I-628 COCH₂CH₃ CH₃ CF₃ H Cl Cl C.I-629 COCH₂CH₃ CH₃ CF₃ H CF₃ CF₃ C.I-630 COCH₂CH₃ CH₃ CF₃ H OCH₃ OCH₃ C.I-631 COCH₂CH₃ CF₃ CH₃ H H CH₃ C.I-632 COCH₂CH₃ CF₃ CH₃ H H Cl C.I-633 COCH₂CH₃ CF₃ CH₃ H H CF₃ C.I-634 COCH₂CH₃ CF₃ CH₃ H H Br C.I-635 COCH₂CH₃ CF₃ CH₃ H H OCH₃ C.I-636 COCH₂CH₃ CF₃ CH₃ H H F C.I-637 COCH₂CH₃ CF₃ CH₃ H CH₃ CH₃ C.I-638 COCH₂CH₃ CF₃ CH₃ H Cl Cl C.I-639 COCH₂CH₃ CF₃ CH₃ H CF₃ CF₃ C.I-640 COCH₂CH₃ CF₃ CH₃ H OCH₃ OCH₃ C.I-641 COCH₂CH₃ F CF₃ H H CH₃ C.I-642 COCH₂CH₃ F CF₃ H H Cl C.I-643 COCH₂CH₃ F CF₃ H H CF₃ C.I-644 COCH₂CH₃ F CF₃ H H Br C.I-645 COCH₂CH₃ F CF₃ H H OCH₃ C.I-646 COCH₂CH₃ F CF₃ H H F C.I-647 COCH₂CH₃ F CF₃ H CH₃ CH₃ C.I-648 COCH₂CH₃ F CF₃ H Cl Cl C.I-649 COCH₂CH₃ F CF₃ H CF₃ CF₃ C.I-650 COCH₂CH₃ F CF₃ H OCH₃ OCH₃ C.I-651 COCH₂CH₃ Cl CF₃ H H CH₃ C.I-652 COCH₂CH₃ Cl CF₃ H H Cl C.I-653 COCH₂CH₃ Cl CF₃ H H CF₃ C.I-654 COCH₂CH₃ Cl CF₃ H H Br C.I-655 COCH₂CH₃ Cl CF₃ H H OCH₃ C.I-656 COCH₂CH₃ Cl CF₃ H H F C.I-657 COCH₂CH₃ Cl CF₃ H CH₃ CH₃ C.I-658 COCH₂CH₃ Cl CF₃ H Cl Cl C.I-659 COCH₂CH₃ Cl CF₃ H CF₃ CF₃ C.I-660 COCH₂CH₃ Cl CF₃ H OCH₃ OCH₃ C.I-661 COCH₂CH₃ CH₃ Cl H H CH₃ C.I-662 COCH₂CH₃ CH₃ Cl H H Cl C.I-663 COCH₂CH₃ CH₃ Cl H H CF₃ C.I-664 COCH₂CH₃ CH₃ Cl H H Br C.I-665 COCH₂CH₃ CH₃ Cl H H OCH₃ C.I-666 COCH₂CH₃ CH₃ Cl H H F C.I-667 COCH₂CH₃ CH₃ Cl H CH₃ CH₃ C.I-668 COCH₂CH₃ CH₃ Cl H Cl Cl C.I-669 COCH₂CH₃ CH₃ Cl H CF₃ CF₃ C.I-670 COCH₂CH₃ CH₃ Cl H OCH₃ OCH₃ C.I-671 COCH₂CH₃ Cl CH₃ H H CH₃ C.I-672 COCH₂CH₃ Cl CH₃ H H Cl C.I-673 COCH₂CH₃ Cl CH₃ H H CF₃ C.I-674 COCH₂CH₃ Cl CH₃ H H Br C.I-675 COCH₂CH₃ Cl CH₃ H H OCH₃ C.I-676 COCH₂CH₃ Cl CH₃ H H F C.I-677 COCH₂CH₃ Cl CH₃ H CH₃ CH₃ C.I-678 COCH₂CH₃ Cl CH₃ H Cl Cl C.I-679 COCH₂CH₃ Cl CH₃ H CF₃ CF₃ C.I-680 COCH₂CH₃ Cl CH₃ H OCH₃ OCH₃ C.I-681 COCH₂CH₃ Cl H Cl H CH₃ C.I-682 COCH₂CH₃ Cl H Cl H Cl C.I-683 COCH₂CH₃ Cl H Cl H CF₃ C.I-684 COCH₂CH₃ Cl H Cl H Br C.I-685 COCH₂CH₃ Cl H Cl H OCH₃ C.I-686 COCH₂CH₃ Cl H Cl H F C.I-687 COCH₂CH₃ Cl H Cl CH₃ CH₃ C.I-688 COCH₂CH₃ Cl H Cl Cl Cl C.I-689 COCH₂CH₃ Cl H Cl CF₃ CF₃ C.I-690 COCH₂CH₃ Cl H Cl OCH₃ OCH₃ C.I-691 COCH₂CH₃ F H F H CH₃ C.I-692 COCH₂CH₃ F H F H Cl C.I-693 COCH₂CH₃ F H F H CF₃ C.I-694 COCH₂CH₃ F H F H Br C.I-695 COCH₂CH₃ F H F H OCH₃ C.I-696 COCH₂CH₃ F H F H F C.I-697 COCH₂CH₃ F H F CH₃ CH₃ C.I-698 COCH₂CH₃ F H F Cl Cl C.I-699 COCH₂CH₃ F H F CF₃ CF₃ C.I-700 COCH₂CH₃ F H F OCH₃ OCH₃ C.I-701 COCH₂CH₃ CH₃ H CH₃ H CH₃ C.I-702 COCH₂CH₃ CH₃ H CH₃ H Cl C.I-703 COCH₂CH₃ CH₃ H CH₃ H CF₃ C.I-704 COCH₂CH₃ CH₃ H CH₃ H Br C.I-705 COCH₂CH₃ CH₃ H CH₃ H OCH₃ C.I-706 COCH₂CH₃ CH₃ H CH₃ H F C.I-707 COCH₂CH₃ CH₃ H CH₃ CH₃ CH₃ C.I-708 COCH₂CH₃ CH₃ H CH₃ Cl Cl C.I-709 COCH₂CH₃ CH₃ H CH₃ CF₃ CF₃ C.I-710 COCH₂CH₃ CH₃ H CH₃ OCH₃ OCH₃ C.I-711 COCH₂CH₃ F H CH₃ H CH₃ C.I-712 COCH₂CH₃ F H CH₃ H Cl C.I-713 COCH₂CH₃ F H CH₃ H CF₃ C.I-714 COCH₂CH₃ F H CH₃ H Br C.I-715 COCH₂CH₃ F H CH₃ H OCH₃ C.I-716 COCH₂CH₃ F H CH₃ H F C.I-717 COCH₂CH₃ F H CH₃ CH₃ CH₃ C.I-718 COCH₂CH₃ F H CH₃ Cl Cl C.I-719 COCH₂CH₃ F H CH₃ CF₃ CF₃ C.I-720 COCH₂CH₃ F H CH₃ OCH₃ OCH₃ C.I-721 COCH₂CH₃ F H CF₃ H CH₃ C.I-722 COCH₂CH₃ F H CF₃ H Cl C.I-723 COCH₂CH₃ F H CF₃ H CF₃ C.I-724 COCH₂CH₃ F H CF₃ H Br C.I-725 COCH₂CH₃ F H CF₃ H OCH₃ C.I-726 COCH₂CH₃ F H CF₃ H F C.I-727 COCH₂CH₃ F H CF₃ CH₃ CH₃ C.I-728 COCH₂CH₃ F H CF₃ Cl Cl C.I-729 COCH₂CH₃ F H CF₃ CF₃ CF₃ C.I-730 COCH₂CH₃ F H CF₃ OCH₃ OCH₃ C.I-731 COCH₂CH₃ F H OCH₃ H CH₃ C.I-732 COCH₂CH₃ F H OCH₃ H Cl C.I-733 COCH₂CH₃ F H OCH₃ H CF₃ C.I-734 COCH₂CH₃ F H OCH₃ H Br C.I-735 COCH₂CH₃ F H OCH₃ H OCH₃ C.I-736 COCH₂CH₃ F H OCH₃ H F C.I-737 COCH₂CH₃ F H OCH₃ CH₃ CH₃ C.I-738 COCH₂CH₃ F H OCH₃ Cl Cl C.I-739 COCH₂CH₃ F H OCH₃ CF₃ CF₃ C.I-740 COCH₂CH₃ F H OCH₃ OCH₃ OCH₃ C.I-741 COCH₂CH₃ F H Br H CH₃ C.I-742 COCH₂CH₃ F H Br H Cl C.I-743 COCH₂CH₃ F H Br H CF₃ C.I-744 COCH₂CH₃ F H Br H Br C.I-745 COCH₂CH₃ F H Br H OCH₃ C.I-746 COCH₂CH₃ F H Br H F C.I-747 COCH₂CH₃ F H Br CH₃ CH₃ C.I-748 COCH₂CH₃ F H Br Cl Cl C.I-749 COCH₂CH₃ F H Br CF₃ CF₃ C.I-750 COCH₂CH₃ F H Br OCH₃ OCH₃ C.I-751 COCH₂CH₃ Br H F H CH₃ C.I-752 COCH₂CH₃ Br H F H Cl C.I-753 COCH₂CH₃ Br H F H CF₃ C.I-754 COCH₂CH₃ Br H F H Br C.I-755 COCH₂CH₃ Br H F H OCH₃ C.I-756 COCH₂CH₃ Br H F H F C.I-757 COCH₂CH₃ Br H F CH₃ CH₃ C.I-758 COCH₂CH₃ Br H F Cl Cl C.I-759 COCH₂CH₃ Br H F CF₃ CF₃ C.I-760 COCH₂CH₃ Br H F OCH₃ OCH₃ C.I-761 COCH₂CH₃ CH₃ H F H CH₃ C.I-762 COCH₂CH₃ CH₃ H F H Cl C.I-763 COCH₂CH₃ CH₃ H F H CF₃ C.I-764 COCH₂CH₃ CH₃ H F H Br C.I-765 COCH₂CH₃ CH₃ H F H OCH₃ C.I-766 COCH₂CH₃ CH₃ H F H F C.I-767 COCH₂CH₃ CH₃ H F CH₃ CH₃ C.I-768 COCH₂CH₃ CH₃ H F Cl Cl C.I-769 COCH₂CH₃ CH₃ H F CF₃ CF₃ C.I-770 COCH₂CH₃ CH₃ H F OCH₃ OCH₃ C.I-771 COCH₂CH₃ OCH₃ H F H CH₃ C.I-772 COCH₂CH₃ OCH₃ H F H Cl C.I-773 COCH₂CH₃ OCH₃ H F H CF₃ C.I-774 COCH₂CH₃ OCH₃ H F H Br C.I-775 COCH₂CH₃ OCH₃ H F H OCH₃ C.I-776 COCH₂CH₃ OCH₃ H F H F C.I-777 COCH₂CH₃ OCH₃ H F CH₃ CH₃ C.I-778 COCH₂CH₃ OCH₃ H F Cl Cl C.I-779 COCH₂CH₃ OCH₃ H F CF₃ CF₃ C.I-780 COCH₂CH₃ OCH₃ H F OCH₃ OCH₃ C.I-781 COCH₂CH₃ CH₃ H Cl H CH₃ C.I-782 COCH₂CH₃ CH₃ H Cl H Cl C.I-783 COCH₂CH₃ CH₃ H Cl H CF₃ C.I-784 COCH₂CH₃ CH₃ H Cl H Br C.I-785 COCH₂CH₃ CH₃ H Cl H OCH₃ C.I-786 COCH₂CH₃ CH₃ H Cl H F C.I-787 COCH₂CH₃ CH₃ H Cl CH₃ CH₃ C.I-788 COCH₂CH₃ CH₃ H Cl Cl Cl C.I-789 COCH₂CH₃ CH₃ H Cl CF₃ CF₃ C.I-790 COCH₂CH₃ CH₃ H Cl OCH₃ OCH₃ C.I-791 COCH₂CH₃ Cl H CH₃ H CH₃ C.I-792 COCH₂CH₃ Cl H CH₃ H Cl C.I-793 COCH₂CH₃ Cl H CH₃ H CF₃ C.I-794 COCH₂CH₃ Cl H CH₃ H Br C.I-795 COCH₂CH₃ Cl H CH₃ H OCH₃ C.I-796 COCH₂CH₃ Cl H CH₃ H F C.I-797 COCH₂CH₃ Cl H CH₃ CH₃ CH₃ C.I-798 COCH₂CH₃ Cl H CH₃ Cl Cl C.I-799 COCH₂CH₃ Cl H CH₃ CF₃ CF₃ C.I-800 COCH₂CH₃ Cl H CH₃ OCH₃ OCH₃ C.I-801 COCH₂C(CH₃)₃ Cl Cl H H CH₃ C.I-802 COCH₂C(CH₃)₃ Cl Cl H H Cl C.I-803 COCH₂C(CH₃)₃ Cl Cl H H CF₃ C.I-804 COCH₂C(CH₃)₃ Cl Cl H H Br C.I-805 COCH₂C(CH₃)₃ Cl Cl H H OCH₃ C.I-806 COCH₂C(CH₃)₃ Cl Cl H H F C.I-807 COCH₂C(CH₃)₃ Cl Cl H CH₃ CH₃ C.I-808 COCH₂C(CH₃)₃ Cl Cl H Cl Cl C.I-809 COCH₂C(CH₃)₃ Cl Cl H CF₃ CF₃ C.I-810 COCH₂C(CH₃)₃ Cl Cl H OCH₃ OCH₃ C.I-811 COCH₂C(CH₃)₃ CH₃ CH₃ H H CH₃ C.I-812 COCH₂C(CH₃)₃ CH₃ CH₃ H H Cl C.I-813 COCH₂C(CH₃)₃ CH₃ CH₃ H H CF₃ C.I-814 COCH₂C(CH₃)₃ CH₃ CH₃ H H Br C.I-815 COCH₂C(CH₃)₃ CH₃ CH₃ H H OCH₃ C.I-816 COCH₂C(CH₃)₃ CH₃ CH₃ H H F C.I-817 COCH₂C(CH₃)₃ CH₃ CH₃ H CH₃ CH₃ C.I-818 COCH₂C(CH₃)₃ CH₃ CH₃ H Cl Cl C.I-819 COCH₂C(CH₃)₃ CH₃ CH₃ H CF₃ CF₃ C.I-820 COCH₂C(CH₃)₃ CH₃ CH₃ H OCH₃ OCH₃ C.I-821 COCH₂C(CH₃)₃ CH₃ CF₃ H H CH₃ C.I-822 COCH₂C(CH₃)₃ CH₃ CF₃ H H Cl C.I-823 COCH₂C(CH₃)₃ CH₃ CF₃ H H CF₃ C.I-824 COCH₂C(CH₃)₃ CH₃ CF₃ H H Br C.I-825 COCH₂C(CH₃)₃ CH₃ CF₃ H H OCH₃ C.I-826 COCH₂C(CH₃)₃ CH₃ CF₃ H H F C.I-827 COCH₂C(CH₃)₃ CH₃ CF₃ H CH₃ CH₃ C.I-828 COCH₂C(CH₃)₃ CH₃ CF₃ H Cl Cl C.I-829 COCH₂C(CH₃)₃ CH₃ CF₃ H CF₃ CF₃ C.I-830 COCH₂C(CH₃)₃ CH₃ CF₃ H OCH₃ OCH₃ C.I-831 COCH₂C(CH₃)₃ CF₃ CH₃ H H CH₃ C.I-832 COCH₂C(CH₃)₃ CF₃ CH₃ H H Cl C.I-833 COCH₂C(CH₃)₃ CF₃ CH₃ H H CF₃ C.I-834 COCH₂C(CH₃)₃ CF₃ CH₃ H H Br C.I-835 COCH₂C(CH₃)₃ CF₃ CH₃ H H OCH₃ C.I-836 COCH₂C(CH₃)₃ CF₃ CH₃ H H F C.I-837 COCH₂C(CH₃)₃ CF₃ CH₃ H CH₃ CH₃ C.I-838 COCH₂C(CH₃)₃ CF₃ CH₃ H Cl Cl C.I-839 COCH₂C(CH₃)₃ CF₃ CH₃ H CF₃ CF₃ C.I-840 COCH₂C(CH₃)₃ CF₃ CH₃ H OCH₃ OCH₃ C.I-841 COCH₂C(CH₃)₃ F CF₃ H H CH₃ C.I-842 COCH₂C(CH₃)₃ F CF₃ H H Cl C.I-843 COCH₂C(CH₃)₃ F CF₃ H H CF₃ C.I-844 COCH₂C(CH₃)₃ F CF₃ H H Br C.I-845 COCH₂C(CH₃)₃ F CF₃ H H OCH₃ C.I-846 COCH₂C(CH₃)₃ F CF₃ H H F C.I-847 COCH₂C(CH₃)₃ F CF₃ H CH₃ CH₃ C.I-848 COCH₂C(CH₃)₃ F CF₃ H Cl Cl C.I-849 COCH₂C(CH₃)₃ F CF₃ H CF₃ CF₃ C.I-850 COCH₂C(CH₃)₃ F CF₃ H OCH₃ OCH₃ C.I-851 COCH₂C(CH₃)₃ Cl CF₃ H H CH₃ C.I-852 COCH₂C(CH₃)₃ Cl CF₃ H H Cl C.I-853 COCH₂C(CH₃)₃ Cl CF₃ H H CF₃ C.I-854 COCH₂C(CH₃)₃ Cl CF₃ H H Br C.I-855 COCH₂C(CH₃)₃ Cl CF₃ H H OCH₃ C.I-856 COCH₂C(CH₃)₃ Cl CF₃ H H F C.I-857 COCH₂C(CH₃)₃ Cl CF₃ H CH₃ CH₃ C.I-858 COCH₂C(CH₃)₃ Cl CF₃ H Cl Cl C.I-859 COCH₂C(CH₃)₃ Cl CF₃ H CF₃ CF₃ C.I-860 COCH₂C(CH₃)₃ Cl CF₃ H OCH₃ OCH₃ C.I-861 COCH₂C(CH₃)₃ CH₃ Cl H H CH₃ C.I-862 COCH₂C(CH₃)₃ CH₃ Cl H H Cl C.I-863 COCH₂C(CH₃)₃ CH₃ Cl H H CF₃ C.I-864 COCH₂C(CH₃)₃ CH₃ Cl H H Br C.I-865 COCH₂C(CH₃)₃ CH₃ Cl H H OCH₃ C.I-866 COCH₂C(CH₃)₃ CH₃ Cl H H F C.I-867 COCH₂C(CH₃)₃ CH₃ Cl H CH₃ CH₃ C.I-868 COCH₂C(CH₃)₃ CH₃ Cl H Cl Cl C.I-869 COCH₂C(CH₃)₃ CH₃ Cl H CF₃ CF₃ C.I-870 COCH₂C(CH₃)₃ CH₃ Cl H OCH₃ OCH₃ C.I-871 COCH₂C(CH₃)₃ Cl CH₃ H H CH₃ C.I-872 COCH₂C(CH₃)₃ Cl CH₃ H H Cl C.I-873 COCH₂C(CH₃)₃ Cl CH₃ H H CF₃ C.I-874 COCH₂C(CH₃)₃ Cl CH₃ H H Br C.I-875 COCH₂C(CH₃)₃ Cl CH₃ H H OCH₃ C.I-876 COCH₂C(CH₃)₃ Cl CH₃ H H F C.I-877 COCH₂C(CH₃)₃ Cl CH₃ H CH₃ CH₃ C.I-878 COCH₂C(CH₃)₃ Cl CH₃ H Cl Cl C.I-879 COCH₂C(CH₃)₃ Cl CH₃ H CF₃ CF₃ C.I-880 COCH₂C(CH₃)₃ Cl CH₃ H OCH₃ OCH₃ C.I-881 COCH₂C(CH₃)₃ Cl H Cl H CH₃ C.I-882 COCH₂C(CH₃)₃ Cl H Cl H Cl C.I-883 COCH₂C(CH₃)₃ Cl H Cl H CF₃ C.I-884 COCH₂C(CH₃)₃ Cl H Cl H Br C.I-885 COCH₂C(CH₃)₃ Cl H Cl H OCH₃ C.I-886 COCH₂C(CH₃)₃ Cl H Cl H F C.I-887 COCH₂C(CH₃)₃ Cl H Cl CH₃ CH₃ C.I-888 COCH₂C(CH₃)₃ Cl H Cl Cl Cl C.I-889 COCH₂C(CH₃)₃ Cl H Cl CF₃ CF₃ C.I-890 COCH₂C(CH₃)₃ Cl H Cl OCH₃ OCH₃ C.I-891 COCH₂C(CH₃)₃ F H F H CH₃ C.I-892 COCH₂C(CH₃)₃ F H F H Cl C.I-893 COCH₂C(CH₃)₃ F H F H CF₃ C.I-894 COCH₂C(CH₃)₃ F H F H Br C.I-895 COCH₂C(CH₃)₃ F H F H OCH₃ C.I-896 COCH₂C(CH₃)₃ F H F H F C.I-897 COCH₂C(CH₃)₃ F H F CH₃ CH₃ C.I-898 COCH₂C(CH₃)₃ F H F Cl Cl C.I-899 COCH₂C(CH₃)₃ F H F CF₃ CF₃ C.I-900 COCH₂C(CH₃)₃ F H F OCH₃ OCH₃ C.I-901 COCH₂C(CH₃)₃ CH₃ H CH₃ H CH₃ C.I-902 COCH₂C(CH₃)₃ CH₃ H CH₃ H Cl C.I-903 COCH₂C(CH₃)₃ CH₃ H CH₃ H CF₃ C.I-904 COCH₂C(CH₃)₃ CH₃ H CH₃ H Br C.I-905 COCH₂C(CH₃)₃ CH₃ H CH₃ H OCH₃ C.I-906 COCH₂C(CH₃)₃ CH₃ H CH₃ H F C.I-907 COCH₂C(CH₃)₃ CH₃ H CH₃ CH₃ CH₃ C.I-908 COCH₂C(CH₃)₃ CH₃ H CH₃ Cl Cl C.I-909 COCH₂C(CH₃)₃ CH₃ H CH₃ CF₃ CF₃ C.I-910 COCH₂C(CH₃)₃ CH₃ H CH₃ OCH₃ OCH₃ C.I-911 COCH₂C(CH₃)₃ F H CH₃ H CH₃ C.I-912 COCH₂C(CH₃)₃ F H CH₃ H Cl C.I-913 COCH₂C(CH₃)₃ F H CH₃ H CF₃ C.I-914 COCH₂C(CH₃)₃ F H CH₃ H Br C.I-915 COCH₂C(CH₃)₃ F H CH₃ H OCH₃ C.I-916 COCH₂C(CH₃)₃ F H CH₃ H F C.I-917 COCH₂C(CH₃)₃ F H CH₃ CH₃ CH₃ C.I-918 COCH₂C(CH₃)₃ F H CH₃ Cl Cl C.I-919 COCH₂C(CH₃)₃ F H CH₃ CF₃ CF₃ C.I-920 COCH₂C(CH₃)₃ F H CH₃ OCH₃ OCH₃ C.I-921 COCH₂C(CH₃)₃ F H CF₃ H CH₃ C.I-922 COCH₂C(CH₃)₃ F H CF₃ H Cl C.I-923 COCH₂C(CH₃)₃ F H CF₃ H CF₃ C.I-924 COCH₂C(CH₃)₃ F H CF₃ H Br C.I-925 COCH₂C(CH₃)₃ F H CF₃ H OCH₃ C.I-926 COCH₂C(CH₃)₃ F H CF₃ H F C.I-927 COCH₂C(CH₃)₃ F H CF₃ CH₃ CH₃ C.I-928 COCH₂C(CH₃)₃ F H CF₃ Cl Cl C.I-929 COCH₂C(CH₃)₃ F H CF₃ CF₃ CF₃ C.I-930 COCH₂C(CH₃)₃ F H CF₃ OCH₃ OCH₃ C.I-931 COCH₂C(CH₃)₃ F H OCH₃ H CH₃ C.I-932 COCH₂C(CH₃)₃ F H OCH₃ H Cl C.I-933 COCH₂C(CH₃)₃ F H OCH₃ H CF₃ C.I-934 COCH₂C(CH₃)₃ F H OCH₃ H Br C.I-935 COCH₂C(CH₃)₃ F H OCH₃ H OCH₃ C.I-936 COCH₂C(CH₃)₃ F H OCH₃ H F C.I-937 COCH₂C(CH₃)₃ F H OCH₃ CH₃ CH₃ C.I-938 COCH₂C(CH₃)₃ F H OCH₃ Cl Cl C.I-939 COCH₂C(CH₃)₃ F H OCH₃ CF₃ CF₃ C.I-940 COCH₂C(CH₃)₃ F H OCH₃ OCH₃ OCH₃ C.I-941 COCH₂C(CH₃)₃ F H Br H CH₃ C.I-942 COCH₂C(CH₃)₃ F H Br H Cl C.I-943 COCH₂C(CH₃)₃ F H Br H CF₃ C.I-944 COCH₂C(CH₃)₃ F H Br H Br C.I-945 COCH₂C(CH₃)₃ F H Br H OCH₃ C.I-946 COCH₂C(CH₃)₃ F H Br H F C.I-947 COCH₂C(CH₃)₃ F H Br CH₃ CH₃ C.I-948 COCH₂C(CH₃)₃ F H Br Cl Cl C.I-949 COCH₂C(CH₃)₃ F H Br CF₃ CF₃ C.I-950 COCH₂C(CH₃)₃ F H Br OCH₃ OCH₃ C.I-951 COCH₂C(CH₃)₃ Br H F H CH₃ C.I-952 COCH₂C(CH₃)₃ Br H F H Cl C.I-953 COCH₂C(CH₃)₃ Br H F H CF₃ C.I-954 COCH₂C(CH₃)₃ Br H F H Br C.I-955 COCH₂C(CH₃)₃ Br H F H OCH₃ C.I-956 COCH₂C(CH₃)₃ Br H F H F C.I-957 COCH₂C(CH₃)₃ Br H F CH₃ CH₃ C.I-958 COCH₂C(CH₃)₃ Br H F Cl Cl C.I-959 COCH₂C(CH₃)₃ Br H F CF₃ CF₃ C.I-960 COCH₂C(CH₃)₃ Br H F OCH₃ OCH₃ C.I-961 COCH₂C(CH₃)₃ CH₃ H F H CH₃ C.I-962 COCH₂C(CH₃)₃ CH₃ H F H Cl C.I-963 COCH₂C(CH₃)₃ CH₃ H F H CF₃ C.I-964 COCH₂C(CH₃)₃ CH₃ H F H Br C.I-965 COCH₂C(CH₃)₃ CH₃ H F H OCH₃ C.I-966 COCH₂C(CH₃)₃ CH₃ H F H F C.I-967 COCH₂C(CH₃)₃ CH₃ H F CH₃ CH₃ C.I-968 COCH₂C(CH₃)₃ CH₃ H F Cl Cl C.I-969 COCH₂C(CH₃)₃ CH₃ H F CF₃ CF₃ C.I-970 COCH₂C(CH₃)₃ CH₃ H F OCH₃ OCH₃ C.I-971 COCH₂C(CH₃)₃ OCH₃ H F H CH₃ C.I-972 COCH₂C(CH₃)₃ OCH₃ H F H Cl C.I-973 COCH₂C(CH₃)₃ OCH₃ H F H CF₃ C.I-974 COCH₂C(CH₃)₃ OCH₃ H F H Br C.I-975 COCH₂C(CH₃)₃ OCH₃ H F H OCH₃ C.I-976 COCH₂C(CH₃)₃ OCH₃ H F H F C.I-977 COCH₂C(CH₃)₃ OCH₃ H F CH₃ CH₃ C.I-978 COCH₂C(CH₃)₃ OCH₃ H F Cl Cl C.I-979 COCH₂C(CH₃)₃ OCH₃ H F CF₃ CF₃ C.I-980 COCH₂C(CH₃)₃ OCH₃ H F OCH₃ OCH₃ C.I-981 COCH₂C(CH₃)₃ CH₃ H Cl H CH₃ C.I-982 COCH₂C(CH₃)₃ CH₃ H Cl H Cl C.I-983 COCH₂C(CH₃)₃ CH₃ H Cl H CF₃ C.I-984 COCH₂C(CH₃)₃ CH₃ H Cl H Br C.I-985 COCH₂C(CH₃)₃ CH₃ H Cl H OCH₃ C.I-986 COCH₂C(CH₃)₃ CH₃ H Cl H F C.I-987 COCH₂C(CH₃)₃ CH₃ H Cl CH₃ CH₃ C.I-988 COCH₂C(CH₃)₃ CH₃ H Cl Cl Cl C.I-989 COCH₂C(CH₃)₃ CH₃ H Cl CF₃ CF₃ C.I-990 COCH₂C(CH₃)₃ CH₃ H Cl OCH₃ OCH₃ C.I-991 COCH₂C(CH₃)₃ Cl H CH₃ H CH₃ C.I-992 COCH₂C(CH₃)₃ Cl H CH₃ H Cl C.I-993 COCH₂C(CH₃)₃ Cl H CH₃ H CF₃ C.I-994 COCH₂C(CH₃)₃ Cl H CH₃ H Br C.I-995 COCH₂C(CH₃)₃ Cl H CH₃ H OCH₃ C.I-996 COCH₂C(CH₃)₃ Cl H CH₃ H F C.I-997 COCH₂C(CH₃)₃ Cl H CH₃ CH₃ CH₃ C.I-998 COCH₂C(CH₃)₃ Cl H CH₃ Cl Cl C.I-999 COCH₂C(CH₃)₃ Cl H CH₃ CF₃ CF₃ C.I- COCH₂C(CH₃)₃ Cl H CH₃ OCH₃ OCH₃ 1000 Preferred Active Compounds II Selected from Group A

With respect to their use in the pesticidal mixtures of the present invention, particular preference is given to the compounds C.II as listed in the paragraphs below.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.1 as defined above is preferably triazemate or primicarb.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.2 as defined above is preferably endosulfan, N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole or vaniliprole or the phenylpyrazole compound II.A^(2.1).

More preferably the compound II is N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole or fipronil.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.3 as defined above is preferably allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin, fenvalerate, flucythrinate, taufluvalinate, silafluofen or tralomethrin.

More preferably the compound II is alpha-cypermethrin or deltamethrin.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.4 as defined above is preferably thiocyclam or from the class of neonicotinoids acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam and AKD-1022; or the allosteric nicotinic acetylcholine receptor agonist spinosad.

More preferably the compound II is clothianidine, imidacloprid or thiamethoxam.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.5 as defined above is preferably abamectin, emamectin benzoate, lepimectin or milbemectin.

More preferably the compound II is abamectin.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.7 as defined above is preferably diafenthiuron.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.8 as defined above is preferably buprofezin.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.10 as defined above is preferably pyridaben or flufenerim.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.11 as defined above is preferably indoxacarb or metaflumizone. More preferably the compound II is metaflumizone.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.12 as defined above is preferably spirodiclofen, spiromesifen or spirotetramat.

More preferably the compound II is spiromesifen or spirotetramat.

With regard to the use in a pesticidal mixture of the present invention, the compound II selected from group A.13 as defined above is preferably amitraz, flonicamid, flubendiamine, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliproler, the anthranil compound II.A^(13.1) or the sulfoximine compounds II.A^(13.2), II.A^(13.3) or II.A^(13.4).

More preferably the compound II is flonicamid, pymetrozine, pyrifluquinazon, chlorantraniliprole or the anthranil compound II.A^(13.1).

Especially preferred are pesticidal mixtures containing N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon as compound II.

Especially preferred are pesticidal mixtures containing N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon as compound II.

Especially preferred are pesticidal mixtures containing acetoprole as compound II.

Especially preferred are pesticidal mixtures containing fipronil as compound II.

Especially preferred are pesticidal mixtures containing alpha-cypermethrin as compound II.

Especially preferred are pesticidal mixtures containing clothianidin as compound II.

Especially preferred are pesticidal mixtures containing imidacloprid as compound II.

Especially preferred are pesticidal mixtures containing thiamethoxam as compound II.

Especially preferred are pesticidal mixtures containing pymetrozine as compound II.

Especially preferred are pesticidal mixtures containing flonicamid as compound II.

Especially preferred are pesticidal mixtures containing spiromesifen as compound II.

Especially preferred are pesticidal mixtures containing spirotetramat as compound II.

Especially preferred are pesticidal mixtures containing pyrifluquinazon as compound II.

Especially preferred are pesticidal mixtures containing chlorantraniliprole as compound II.

Especially preferred are pesticidal mixtures containing the anthranilamid compound II.A^(13.1)

as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximine compound II.A^(13.2)

as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximine compound II.A^(13.3)

as compound II.

Especially preferred are pesticidal mixtures containing the sulfoximine compound II.A^(13.4)

as compound II.

Preferred Mixtures According to the Invention

Especially preferred are inventive mixtures wherein the compound II of group A is acetoprol and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is fipronil and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is alpha-cypermethrin and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is deltamethrin and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is clothianidin and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is imidacloprid and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is thiamethoxam and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is abamectin and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is pymetrozine and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is flonicamid and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is diafenthiuron and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is buprofezin and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is pyridaben and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is flufenerim and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is metaflumizone and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is spiromesifen and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is spirotetramat and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is pyrifluquinazon and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is chlorantraniliprole and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is the anthranilamid compound II.A^(13.1) and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is the sulfoximine compound II.A^(13.2) and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is the sulfoximine compound II.A^(13.3) and the compound I of formula I is a compound of Table C.

Especially preferred are inventive mixtures wherein the compound II of group A is the sulfoximine compound II.A^(13.4) and the compound I of formula I is a compound of Table C.

The following table M represents preferred combinations of the active compounds I of formula I as defined in table C and the active compounds II of group A in mixtures according to the invention:

TABLE M Mixture Compound I Compound-II Mixture Compound I Compound II M.1 C.I-1 acetoprole M.113 C.I-1 diafenthiuron M.2 C.I-7 acetoprole M.114 C.I-7 diafenthiuron M.3 C.I-11 acetoprole M.115 C.I-11 diafenthiuron M.4 C.I-17 acetoprole M.116 C.I-17 diafenthiuron M.5 C.I-21 acetoprole M.117 C.I-21 diafenthiuron M.6 C.I-27 acetoprole M.118 C.I-27 diafenthiuron M.7 C.I-51 acetoprole M.119 C.I-51 diafenthiuron M.8 C.I-57 acetoprole M.120 C.I-57 diafenthiuron M.9 C.I-81 acetoprole M.121 C.I-81 diafenthiuron M.10 C.I-87 acetoprole M.122 C.I-87 diafenthiuron M.11 C.I-91 acetoprole M.123 C.I-91 diafenthiuron M.12 C.I-97 acetoprole M.124 C.I-97 diafenthiuron M.13 C.I-101 acetoprole M.125 C.I-101 diafenthiuron M.14 C.I-107 acetoprole M.126 C.I-107 diafenthiuron M.15 C.I-201 acetoprole M.127 C.I-201 diafenthiuron M.16 C.I-207 acetoprole M.128 C.I-207 diafenthiuron M.17 C.I-211 acetoprole M.129 C.I-211 diafenthiuron M.18 C.I-217 acetoprole M.130 C.I-217 diafenthiuron M.19 C.I-221 acetoprole M.131 C.I-221 diafenthiuron M.20 C.I-227 acetoprole M.132 C.I-227 diafenthiuron M.21 C.I-251 acetoprole M.133 C.I-251 diafenthiuron M.22 C.I-257 acetoprole M.134 C.I-257 diafenthiuron M.23 C.I-281 acetoprole M.135 C.I-281 diafenthiuron M.24 C.I-287 acetoprole M.136 C.I-287 diafenthiuron M.25 C.I-291 acetoprole M.137 C.I-291 diafenthiuron M.26 C.I-297 acetoprole M.138 C.I-297 diafenthiuron M.27 C.I-301 acetoprole M.139 C.I-301 diafenthiuron M.28 C.I-307 acetoprole M.140 C.I-307 diafenthiuron M.29 C.I-1 fipronil M.141 C.I-1 buprofezin M.30 C.I-7 fipronil M.142 C.I-7 buprofezin M.31 C.I-11 fipronil M.143 C.I-11 buprofezin M.32 C.I-17 fipronil M.144 C.I-17 buprofezin M.33 C.I-21 fipronil M.145 C.I-21 buprofezin M.34 C.I-27 fipronil M.146 C.I-27 buprofezin M.35 C.I-51 fipronil M.147 C.I-51 buprofezin M.36 C.I-57 fipronil M.148 C.I-57 buprofezin M.37 C.I-81 fipronil M.149 C.I-81 buprofezin M.38 C.I-87 fipronil M.150 C.I-87 buprofezin M.39 C.I-91 fipronil M.151 C.I-91 buprofezin M.40 C.I-97 fipronil M.152 C.I-97 buprofezin M.41 C.I-101 fipronil M.153 C.I-101 buprofezin M.42 C.I-107 fipronil M.154 C.I-107 buprofezin M.43 C.I-201 fipronil M.155 C.I-201 buprofezin M.44 C.I-207 fipronil M.156 C.I-207 buprofezin M.45 C.I-211 fipronil M.157 C.I-211 buprofezin M.46 C.I-217 fipronil M.158 C.I-217 buprofezin M.47 C.I-221 fipronil M.159 C.I-221 buprofezin M.48 C.I-227 fipronil M.160 C.I-227 buprofezin M.49 C.I-251 fipronil M.161 C.I-251 buprofezin M.50 C.I-257 fipronil M.162 C.I-257 buprofezin M.51 C.I-281 fipronil M.163 C.I-281 buprofezin M.52 C.I-287 fipronil M.164 C.I-287 buprofezin M.53 C.I-291 fipronil M.165 C.I-291 buprofezin M.54 C.I-297 fipronil M.166 C.I-297 buprofezin M.55 C.I-301 fipronil M.167 C.I-301 buprofezin M.56 C.I-307 fipronil M.168 C.I-307 buprofezin M.57 C.I-1 imidacloprid M.169 C.I-1 pyridaben M.58 C.I-7 imidacloprid M.170 C.I-7 pyridaben M.59 C.I-11 imidacloprid M.171 C.I-11 pyridaben M.60 C.I-17 imidacloprid M.172 C.I-17 pyridaben M.61 C.I-21 imidacloprid M.173 C.I-21 pyridaben M.62 C.I-27 imidacloprid M.174 C.I-27 pyridaben M.63 C.I-51 imidacloprid M.175 C.I-51 pyridaben M.64 C.I-57 imidacloprid M.176 C.I-57 pyridaben M.65 C.I-81 imidacloprid M.177 C.I-81 pyridaben M.66 C.I-87 imidacloprid M.178 C.I-87 pyridaben M.67 C.I-91 imidacloprid M.179 C.I-91 pyridaben M.68 C.I-97 imidacloprid M.180 C.I-97 pyridaben M.69 C.I-101 imidacloprid M.181 C.I-101 pyridaben M.70 C.I-107 imidacloprid M.182 C.I-107 pyridaben M.71 C.I-201 imidacloprid M.183 C.I-201 pyridaben M.72 C.I-207 imidacloprid M.184 C.I-207 pyridaben M.73 C.I-211 imidacloprid M.185 C.I-211 pyridaben M.74 C.I-217 imidacloprid M.186 C.I-217 pyridaben M.75 C.I-221 imidacloprid M.187 C.I-221 pyridaben M.76 C.I-227 imidacloprid M.188 C.I-227 pyridaben M.77 C.I-251 imidacloprid M.189 C.I-251 pyridaben M.78 C.I-257 imidacloprid M.190 C.I-257 pyridaben M.79 C.I-281 imidacloprid M.191 C.I-281 pyridaben M.80 C.I-287 imidacloprid M.192 C.I-287 pyridaben M.81 C.I-291 imidacloprid M.193 C.I-291 pyridaben M.82 C.I-297 imidacloprid M.194 C.I-297 pyridaben M.83 C.I-301 imidacloprid M.195 C.I-301 pyridaben M.84 C.I-307 imidacloprid M.196 C.I-307 pyridaben M.85 C.I-1 abamectin M.197 C.I-1 spiromesifen M.86 C.I-7 abamectin M.198 C.I-7 spiromesifen M.87 C.I-11 abamectin M.199 C.I-11 spiromesifen M.88 C.I-17 abamectin M.200 C.I-17 spiromesifen M.89 C.I-21 abamectin M.201 C.I-21 spiromesifen M.90 C.I-27 abamectin M.202 C.I-27 spiromesifen M.91 C.I-51 abamectin M.203 C.I-51 spiromesifen M.92 C.I-57 abamectin M.204 C.I-57 spiromesifen M.93 C.I-81 abamectin M.205 C.I-81 spiromesifen M.94 C.I-87 abamectin M.206 C.I-87 spiromesifen M.95 C.I-91 abamectin M.207 C.I-91 spiromesifen M.96 C.I-97 abamectin M.208 C.I-97 spiromesifen M.97 C.I-101 abamectin M.209 C.I-101 spiromesifen M.98 C.I-107 abamectin M.210 C.I-107 spiromesifen M.99 C.I-201 abamectin M.211 C.I-201 spiromesifen M.100 C.I-207 abamectin M.212 C.I-207 spiromesifen M.101 C.I-211 abamectin M.213 C.I-211 spiromesifen M.102 C.I-217 abamectin M.214 C.I-217 spiromesifen M.103 C.I-221 abamectin M.215 C.I-221 spiromesifen M.104 C.I-227 abamectin M.216 C.I-227 spiromesifen M.105 C.I-251 abamectin M.217 C.I-251 spiromesifen M.106 C.I-257 abamectin M.218 C.I-257 spiromesifen M.107 C.I-281 abamectin M.219 C.I-281 spiromesifen M.108 C.I-287 abamectin M.220 C.I-287 spiromesifen M.109 C.I-291 abamectin M.221 C.I-291 spiromesifen M.110 C.I-297 abamectin M.222 C.I-297 spiromesifen M.111 C.I-301 abamectin M.223 C.I-301 spiromesifen M.112 C.I-307 abamectin M.224 C.I-307 spiromesifen M.113 C.I-1 anthranilamid M.225 C.I-1 chlorantraniliprole II.A^(13.1) M.114 C.I-7 anthranilamid M.226 C.I-7 chlorantraniliprole II.A^(13.1) M.115 C.I-11 anthranilamid M.227 C.I-11 chlorantraniliprole II.A^(13.1) M.116 C.I-17 anthranilamid M.228 C.I-17 chlorantraniliprole II.A^(13.1) M.117 C.I-21 anthranilamid M.229 C.I-21 chlorantraniliprole II.A^(13.1) M.118 C.I-27 anthranilamid M.230 C.I-27 chlorantraniliprole II.A^(13.1) M.119 C.I-51 anthranilamid M.231 C.I-51 chlorantraniliprole II.A^(13.1) M.120 C.I-57 anthranilamid M.232 C.I-57 chlorantraniliprole II.A^(13.1) M.121 C.I-81 anthranilamid M.233 C.I-81 chlorantraniliprole II.A^(13.1) M.122 C.I-87 anthranilamid M.234 C.I-87 chlorantraniliprole II.A^(13.1) M.123 C.I-91 anthranilamid M.235 C.I-91 chlorantraniliprole II.A^(13.1) M.124 C.I-97 anthranilamid M.236 C.I-97 chlorantraniliprole II.A^(13.1) M.125 C.I-101 anthranilamid M.237 C.I-101 chlorantraniliprole II.A^(13.1) M.126 C.I-107 anthranilamid M.238 C.I-107 chlorantraniliprole II.A^(13.1) M.127 C.I-201 anthranilamid M.239 C.I-201 chlorantraniliprole II.A^(13.1) M.128 C.I-207 anthranilamid M.240 C.I-207 chlorantraniliprole II.A^(13.1) M.129 C.I-211 anthranilamid M.241 C.I-211 chlorantraniliprole II.A^(13.1) M.130 C.I-217 anthranilamid M.242 C.I-217 chlorantraniliprole II.A^(13.1) M.131 C.I-221 anthranilamid M.243 C.I-221 chlorantraniliprole II.A^(13.1) M.132 C.I-227 anthranilamid M.244 C.I-227 chlorantraniliprole II.A^(13.1) M.133 C.I-251 anthranilamid M.245 C.I-251 chlorantraniliprole II.A^(13.1) M.134 C.I-257 anthranilamid M.246 C.I-257 chlorantraniliprole II.A^(13.1) M.135 C.I-281 anthranilamid M.247 C.I-281 chlorantraniliprole II.A^(13.1) M.136 C.I-287 anthranilamid M.248 C.I-287 chlorantraniliprole II.A^(13.1) M.137 C.I-291 anthranilamid M.249 C.I-291 chlorantraniliprole II.A^(13.1) M.138 C.I-297 anthranilamid M.250 C.I-297 chlorantraniliprole II.A^(13.1) M.139 C.I-301 anthranilamid M.251 C.I-301 chlorantraniliprole II.A^(13.1) M.140 C.I-307 anthranilamid M.252 C.I-307 chlorantraniliprole II.A^(13.1) M.141 C.I-1 deltamethrin M.253 C.I-1 flufenerim M.142 C.I-7 deltamethrin M.254 C.I-7 flufenerim M.143 C.I-11 deltamethrin M.255 C.I-11 flufenerim M.144 C.I-17 deltamethrin M.256 C.I-17 flufenerim M.145 C.I-21 deltamethrin M.257 C.I-21 flufenerim M.146 C.I-27 deltamethrin M.258 C.I-27 flufenerim M.147 C.I-51 deltamethrin M.259 C.I-51 flufenerim M.148 C.I-57 deltamethrin M.260 C.I-57 flufenerim M.149 C.I-81 deltamethrin M.261 C.I-81 flufenerim M.150 C.I-87 deltamethrin M.262 C.I-87 flufenerim M.151 C.I-91 deltamethrin M.263 C.I-91 flufenerim M.152 C.I-97 deltamethrin M.264 C.I-97 flufenerim M.153 C.I-101 deltamethrin M.265 C.I-101 flufenerim M.154 C.I-107 deltamethrin M.266 C.I-107 flufenerim M.155 C.I-201 deltamethrin M.267 C.I-201 flufenerim M.156 C.I-207 deltamethrin M.268 C.I-207 flufenerim M.157 C.I-211 deltamethrin M.269 C.I-211 flufenerim M.158 C.I-217 deltamethrin M.270 C.I-217 flufenerim M.159 C.I-221 deltamethrin M.271 C.I-221 flufenerim M.160 C.I-227 deltamethrin M.272 C.I-227 flufenerim M.161 C.I-251 deltamethrin M.273 C.I-251 flufenerim M.162 C.I-257 deltamethrin M.274 C.I-257 flufenerim M.163 C.I-281 deltamethrin M.275 C.I-281 flufenerim M.164 C.I-287 deltamethrin M.276 C.I-287 flufenerim M.165 C.I-291 deltamethrin M.277 C.I-291 flufenerim M.166 C.I-297 deltamethrin M.278 C.I-297 flufenerim M.167 C.I-301 deltamethrin M.279 C.I-301 flufenerim M.168 C.I-307 deltamethrin M.280 C.I-307 flufenerim M.169 C.I-1 metaflumizone M.281 C.I-1 α-cypermethrin M.170 C.I-7 metaflumizone M.282 C.I-7 α-cypermethrin M.171 C.I-11 metaflumizone M.283 C.I-11 α-cypermethrin M.172 C.I-17 metaflumizone M.284 C.I-17 α-cypermethrin M.173 C.I-21 metaflumizone M.285 C.I-21 α-cypermethrin M.174 C.I-27 metaflumizone M.286 C.I-27 α-cypermethrin M.175 C.I-51 metaflumizone M.287 C.I-51 α-cypermethrin M.176 C.I-57 metaflumizone M.288 C.I-57 α-cypermethrin M.177 C.I-81 metaflumizone M.289 C.I-81 α-cypermethrin M.178 C.I-87 metaflumizone M.290 C.I-87 α-cypermethrin M.179 C.I-91 metaflumizone M.291 C.I-91 α-cypermethrin M.180 C.I-97 metaflumizone M.292 C.I-97 α-cypermethrin M.181 C.I-101 metaflumizone M.293 C.I-101 α-cypermethrin M.182 C.I-107 metaflumizone M.294 C.I-107 α-cypermethrin M.183 C.I-201 metaflumizone M.295 C.I-201 α-cypermethrin M.184 C.I-207 metaflumizone M.296 C.I-207 α-cypermethrin M.185 C.I-211 metaflumizone M.297 C.I-211 α-cypermethrin M.186 C.I-217 metaflumizone M.298 C.I-217 α-cypermethrin M.187 C.I-221 metaflumizone M.299 C.I-221 α-cypermethrin M.188 C.I-227 metaflumizone M.300 C.I-227 α-cypermethrin M.189 C.I-251 metaflumizone M.301 C.I-251 α-cypermethrin M.190 C.I-257 metaflumizone M.302 C.I-257 α-cypermethrin M.191 C.I-281 metaflumizone M.303 C.I-281 α-cypermethrin M.192 C.I-287 metaflumizone M.304 C.I-287 α-cypermethrin M.193 C.I-291 metaflumizone M.305 C.I-291 α-cypermethrin M.194 C.I-297 metaflumizone M.306 C.I-297 α-cypermethrin M.195 C.I-301 metaflumizone M.307 C.I-301 α-cypermethrin M.196 C.I-307 metaflumizone M.308 C.I-307 α-cypermethrin M.197 C.I-1 clothianidine M.309 C.I-1 thiamethoxam M.198 C.I-7 clothianidine M.310 C.I-7 thiamethoxam M.199 C.I-11 clothianidine M.311 C.I-11 thiamethoxam M.200 C.I-17 clothianidine M.312 C.I-17 thiamethoxam M.201 C.I-21 clothianidine M.313 C.I-21 thiamethoxam M.202 C.I-27 clothianidine M.314 C.I-27 thiamethoxam M.203 C.I-51 clothianidine M.315 C.I-51 thiamethoxam M.204 C.I-57 clothianidine M.316 C.I-57 thiamethoxam M.205 C.I-81 clothianidine M.317 C.I-81 thiamethoxam M.206 C.I-87 clothianidine M.318 C.I-87 thiamethoxam M.207 C.I-91 clothianidine M.319 C.I-91 thiamethoxam M.208 C.I-97 clothianidine M.320 C.I-97 thiamethoxam M.209 C.I-101 clothianidine M.321 C.I-101 thiamethoxam M.210 C.I-107 clothianidine M.322 C.I-107 thiamethoxam M.211 C.I-201 clothianidine M.323 C.I-201 thiamethoxam M.212 C.I-207 clothianidine M.324 C.I-207 thiamethoxam M.213 C.I-211 clothianidine M.325 C.I-211 thiamethoxam M.214 C.I-217 clothianidine M.326 C.I-217 thiamethoxam M.215 C.I-221 clothianidine M.327 C.I-221 thiamethoxam M.216 C.I-227 clothianidine M.328 C.I-227 thiamethoxam M.217 C.I-251 clothianidine M.329 C.I-251 thiamethoxam M.218 C.I-257 clothianidine M.330 C.I-257 thiamethoxam M.219 C.I-281 clothianidine M.331 C.I-281 thiamethoxam M.220 C.I-287 clothianidine M.332 C.I-287 thiamethoxam M.221 C.I-291 clothianidine M.333 C.I-291 thiamethoxam M.222 C.I-297 clothianidine M.334 C.I-297 thiamethoxam M.223 C.I-301 clothianidine M.335 C.I-301 thiamethoxam M.224 C.I-307 clothianidine M.336 C.I-307 thiamethoxam M.225 C.I-1 flonicamid M.337 C.I-1 spirotetramat M.226 C.I-7 flonicamid M.338 C.I-7 spirotetramat M.227 C.I-11 flonicamid M.339 C.I-11 spirotetramat M.228 C.I-17 flonicamid M.340 C.I-17 spirotetramat M.229 C.I-21 flonicamid M.341 C.I-21 spirotetramat M.230 C.I-27 flonicamid M.342 C.I-27 spirotetramat M.231 C.I-51 flonicamid M.343 C.I-51 spirotetramat M.232 C.I-57 flonicamid M.344 C.I-57 spirotetramat M.233 C.I-81 flonicamid M.345 C.I-81 spirotetramat M.234 C.I-87 flonicamid M.346 C.I-87 spirotetramat M.235 C.I-91 flonicamid M.347 C.I-91 spirotetramat M.236 C.I-97 flonicamid M.348 C.I-97 spirotetramat M.237 C.I-101 flonicamid M.349 C.I-101 spirotetramat M.238 C.I-107 flonicamid M.350 C.I-107 spirotetramat M.239 C.I-201 flonicamid M.351 C.I-201 spirotetramat M.240 C.I-207 flonicamid M.352 C.I-207 spirotetramat M.241 C.I-211 flonicamid M.353 C.I-211 spirotetramat M.242 C.I-217 flonicamid M.354 C.I-217 spirotetramat M.243 C.I-221 flonicamid M.355 C.I-221 spirotetramat M.244 C.I-227 flonicamid M.356 C.I-227 spirotetramat M.245 C.I-251 flonicamid M.357 C.I-251 spirotetramat M.246 C.I-257 flonicamid M.358 C.I-257 spirotetramat M.247 C.I-281 flonicamid M.359 C.I-281 spirotetramat M.248 C.I-287 flonicamid M.360 C.I-287 spirotetramat M.249 C.I-291 flonicamid M.361 C.I-291 spirotetramat M.250 C.I-297 flonicamid M.362 C.I-297 spirotetramat M.251 C.I-301 flonicamid M.363 C.I-301 spirotetramat M.252 C.I-307 flonicamid M.364 C.I-307 spirotetramat M.253 C.I-1 pymetrozine M.365 C.I-1 pyrifluquinazone M.254 C.I-7 pymetrozine M.366 C.I-7 pyrifluquinazone M.255 C.I-11 pymetrozine M.367 C.I-11 pyrifluquinazone M.256 C.I-17 pymetrozine M.368 C.I-17 pyrifluquinazone M.257 C.I-21 pymetrozine M.369 C.I-21 pyrifluquinazone M.258 C.I-27 pymetrozine M.370 C.I-27 pyrifluquinazone M.259 C.I-51 pymetrozine M.371 C.I-51 pyrifluquinazone M.260 C.I-57 pymetrozine M.372 C.I-57 pyrifluquinazone M.261 C.I-81 pymetrozine M.373 C.I-81 pyrifluquinazone M.262 C.I-87 pymetrozine M.374 C.I-87 pyrifluquinazone M.263 C.I-91 pymetrozine M.375 C.I-91 pyrifluquinazone M.264 C.I-97 pymetrozine M.376 C.I-97 pyrifluquinazone M.265 C.I-101 pymetrozine M.377 C.I-101 pyrifluquinazone M.266 C.I-107 pymetrozine M.378 C.I-107 pyrifluquinazone M.267 C.I-201 pymetrozine M.379 C.I-201 pyrifluquinazone M.268 C.I-207 pymetrozine M.380 C.I-207 pyrifluquinazone M.269 C.I-211 pymetrozine M.381 C.I-211 pyrifluquinazone M.270 C.I-217 pymetrozine M.382 C.I-217 pyrifluquinazone M.271 C.I-221 pymetrozine M.383 C.I-221 pyrifluquinazone M.272 C.I-227 pymetrozine M.384 C.I-227 pyrifluquinazone M.273 C.I-251 pymetrozine M.385 C.I-251 pyrifluquinazone M.274 C.I-257 pymetrozine M.386 C.I-257 pyrifluquinazone M.275 C.I-281 pymetrozine M.387 C.I-281 pyrifluquinazone M.276 C.I-287 pymetrozine M.388 C.I-287 pyrifluquinazone M.277 C.I-291 pymetrozine M.389 C.I-291 pyrifluquinazone M.278 C.I-297 pymetrozine M.390 C.I-297 pyrifluquinazone M.279 C.I-301 pymetrozine M.391 C.I-301 pyrifluquinazone M.280 C.I-307 pymetrozine M.392 C.I-307 pyrifluquinazone

General Preparation Methods of Compounds of Formula I

Aminothiazoline compounds of formula I of the present invention can be prepared starting from amines of the general formula II:

Amines of the general formula II can be prepared e.g. by addition of appropriately substituted anion equivalents, for examples of organometallic compounds V, to appropriately substituted C═N bond containing compounds IV (cf. for example Chem. Rev. 1998, 98, 1407-1438):

Starting imines IV can for example be prepared by methods familiar to an Organic chemist from the corresponding aldehydes III by reaction with amines in the presence of a dehydrating agent or from nitriles by reduction (e.g. J. Org. Chem. 1990, 55, 4199-4200) and are well known in the art. Starting imines IV include also chiral compounds as for example described in Tetrahedron 1999, 55, 8883-8904.

An example for the latter method is given in unpublished U.S. application U.S. 60/817,973, preparation examples 3.2 and 3.3. Another example for the addition of organometallic compounds to imines has been described in unpublished U.S. 60/817,973 for related compounds by reaction of in situ generated trimethylsilylimines with benzyl magnesium compounds (cf. example 1 in unpublished 60/817,973 and example given below).

Amines of the general formula II can also be prepared e.g. by addition of appropriately substituted organometallic compounds V to nitriles VI followed by reduction of the intermediate imines as demonstrated in the following scheme:

A further preparation of amines of the general formula II involves the addition of benzylic compounds to masked benzylamines such as the substitution reaction of benzyl halides X with e.g. substituted benzyl benzophenone imines IX in the presence of base followed be the liberation of the amine or its salt by means of e.g. acids as described for similar compounds in unpublished international application PCT/EP2006/069525, example P.I.1.b.). Substituted benzophenone imines can be obtained e.g. by condensation of amines VII with benzophenone VIII.

A further preparation of amines of the general formula II involves the Hofmann degradation of carboxamides XI as demonstrated in the following scheme:

A general method for the preparation of compounds similar to formula II by such methods has been described in U.S. Pat. No. 4,536,599.

The starting carboxamides XI can be prepared as described in the above cited publication or by conventional methods known by the person skilled in the art.

Examples are given in the following scheme:

Such nitriles XIII can for example be prepared from their corresponding halides XII by substitution reaction with cyanides such as potassium or sodium cyanide in appropriate solvents.

Amines of the general formula II can also be prepared e.g. by reductive amination of their corresponding ketones XV as outlined in the following scheme:

Reductive amination can be accomplished by several means, e.g. reaction with ammonia and hydrogen at higher pressure in an autoclave starting from either ketones XV of oximes XVI, cf. for example WO 2005/063724.

Preparation of the corresponding ketones XV are various and very well known to those skilled in the art. Examples among other methods involve e.g. the addition of benzyl organometallic compounds or anions to appropriately substituted benzoic acids or their esters. Alternatively the addition of such organometallic compounds/anions V to corresponding benzaldehydes III followed by oxidation of the resulting alcohols XVII as demonstrated below. Another route is the addition of phenylmetals XVIII to appropriately substituted phenyl acetaldehyde XIX

Preparation of such ketones XVII is also possible via the addition of benzyl halides X to masked aldehydes such as XX or XXI utilizing the umpolung reactions as demonstrated in the scheme below:

A further method involves the reaction of appropriately substituted nitromethyl benzene compounds XXII with an appropriately substituted benzaldehyde III. The corresponding nitro stilbenes XXIII can be converted to amines of the general formula II by reduction as described e.g. in Journal of Pharmaceutical Sciences 1985, 73 (11), 1548-1550. An example of this type of reaction is also given in unpublished international application PCT/EP2006/069525, see example P.I.1.a for similar compounds structures).

Aminoazolines of the general formula I can be prepared e.g. by addition of chloro-ethyliso(-thio)cyanate XXIV to amines II and subsequent cyclization of compounds XXV in the presence of base (cf. WO 2005/063724):

Aminoazolines of the general formula I can also be prepared e.g. by reaction of amines II with (thio-)phosgene or (thio-)phosgene type reagents or reaction of the corresponding iso(thio)cyanates with aminoethanol and cyclisation in the presence of acids and or dehydrating agents (cf. eg. WO 2005/063724 or unpublished international application PCT/EP2006/069525).

Likewise, aminothiazolines of the general formula I can be prepared by converting amines of the general formula I or a salt thereof to the corresponding aminothiocarbonylaminoethane compound, by reacting the amine with acetoxyethyl isothiocyanates and subsequent saponification as described e.g. in unpublished international application PCT/EP2006/069525 for the preparation of similar compounds. Acetoxyethyl isothiocyanate can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51, 112-117.

Aminothiazolines of the general formula I can also be prepared e.g. by reacting an appropriately protected benzylamino thiazoline XXVI with benzylhalides X in the presence of base and subsequent deprotection of compounds XXVII for example in the presence of mineralic of trifluoroacetic acid as outlined below or described for similar compounds in unpublished international application PCT/EP2006/069525, example P.II.1 and PII.2.

Aminothiazolines of the general formula Ib can also be obtained by reaction of aminothiazolines Ia with e.g. acetyl chloride or acetic acid anhydride in the presence of base.

Pests

The mixtures of the active compounds I and II, or the active compounds I and II used simultaneously, that is jointly or separately, exhibit outstanding action against pests from the following orders:

Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chematobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis, beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria, flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus, cockroaches (Blattaria—Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus. ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina, Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa, fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata, millipedes (Diplopoda), e.g. Narceus spp., Earwigs (Dermaptera), e.g. forficula auricularia, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. Plant parasitic nematodes such as root-knot nematodes, Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera pallida, Globodera tabacum and other Globodera species, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; seed gall nematodes, Anguina funesta, Anguina tritici and other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoides ritzemabosi and other Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, and Mesocriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and other Ditylenchus species; awl nematodes, Dolichodorus species; spiral nematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus and other Helicotylenchus species, Rotylenchus robustus and other Rotylenchus species; sheath nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; lance nematodes, Hoplolaimus columbus, Hoplolaimus galeatus and other Hoplolaimus species; false root-knot nematodes, Nacobbus aberrans and other Nacobbus species; needle nematodes, Longidorus elongates and other Longidorus species; pin nematodes, Paratylenchus species; lesion nematodes, Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae and other Pratylenchus species; Radinaphelenchus cocophilus and other Radinaphelenchus species; burrowing nematodes, Radopholus similis and other Radopholus species; reniform nematodes, Rotylenchulus reniformis and other Rotylenchulus species; Scutellonema species; stubby root nematodes, Trichodorus primitivus and other Trichodorus species; Paratrichodorus minor and other Paratrichodorus species; stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species and Merlinius species; citrus nematodes, Tylenchulus semipenetrans and other Tylenchulus species; dagger nematodes, Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and other Xiphinema species; and other plant parasitic nematode species.

Moreover, the inventive mixtures are especially useful for the control of Lepidoptera, Coleoptera, Diptera, Thysanoptera and Hymenoptera.

In particular the inventive mixtures are useful for the control of Thysanoptera and Hymenoptera, especially Hymenoptera.

Formulations

The mixtures according to the present invention can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compounds according to the invention.

The formulations are prepared in a known manner (see e.g. for review U.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, U.S. Pat. No. 4,172,714, U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S. Pat. No. 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001, 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti-foaming agents, anti-freezing agents, for seed treatment formulation also optionally gelling agents.

Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP(N-methyl-pyrrolidone), NOP(N-octylpyrrolidone)), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.

Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).

Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.

A suitable preservative is e.g. dichlorophen.

An example of a gelling agent is carrageen (Satiagel®)

Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.

Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compounds. In this case, the active compounds are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).

For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compounds by weight, preferably 0.1 to 40% by weight.

The mixtures of the present invention can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1% per weight.

The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.

The following are examples of formulations:

1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.

A) Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolve(s) upon dilution with water, whereby a formulation with 10% (w/w) of active compound(s) is obtained.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compound(s) are dissolved in 7 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)

75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 75% (w/w) of active compound(s) is obtained.

H) Gel-Formulation (GF)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.

I) Dustable Powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s).

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound(s) is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound(s) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.

K) ULV Solutions (UL)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.

Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.

Applications

The compounds I and the one or more compound(s) II can be applied simultaneously, that is jointly or separately, or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.

The mixtures of the invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a insecticidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.

The compounds I and the one or more compound(s) II are usually applied in a weight ratio of from 500:1 to 1:100, preferably from 20:1 to 1:50, in particular from 5:1 to 1:20. Depending on the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.

The mixtures according to the invention are effective through both contact and ingestion.

According to a preferred embodiment of the invention, the mixtures according to the present invention are employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.

According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the mixtures according to the present invention are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).

Another aspect of the present invention is when preparing the mixtures, it is preferred to employ the pure active compounds I and II, to which further active compounds, e.g. against harmful fungi or having herbicidal activity, or growth-regulating agents or fertilizers can be added.

Compositions of this invention may further contain other active ingredients than those listed above. For example fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

The mixtures according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive mixtures or of compositions comprising the mixtures.

“Locus” means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.

In general, “pesticidally effective amount” means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures and/or compositions used in the invention. A pesticidally effective amount of the mixtures and/or compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

The inventive mixtures or compositions of these mixtures can also be employed for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

The inventive mixtures are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait.

According to another preferred embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the inventive mixtures are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and/or sex pheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with the inventive mixtures and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, non-wovens, netting material or foils and tarpaulins preferably comprise a composition including the inventive mixtures, optionally a repellent and at least one binder.

The inventive mixtures and the compositions comprising them can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient(s) ranges from 0.0001 to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound(s) per m² treated material, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.

For use in bait compositions, the typical content of active ingredient(s) is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.

For use in spray compositions, the content of the mixture of the active ingredients is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the mixture of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the plant propagation material.

The mixtures of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants.

Plants which can be treated with the inventive mixtures include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.

The term “plant propagation material” is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be mentioned. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

The term “cultivated plants” is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.

The term “cultivated plants” is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hydroxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e.g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e.g. U.S. Pat. No. 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e.g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).

The term “cultivated plants” is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ä-endotoxins, e.g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of insects, especially to beetles (Coeloptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

The term “cultivated plants” is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called “pathogenesis-related proteins” (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lyso-zym (e.g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

The term “cultivated plants” is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environ-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

The term “cultivated plants” is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for example oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rape).

The term “cultivated plants” is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato).

Some of the inventive mixtures have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests.

Seed Treatment

The mixtures according to the present invention are therefore suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects.

The protection of the resulting plant's roots and shoots is preferred.

More preferred is the protection of resulting plant's shoots from piercing and sucking insects.

The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with mixtures according to the present invention. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

The present invention also comprises seeds coated with or containing the active compound(s). The term “coated with and/or containing” generally signifies that the active ingredient(s) are for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product are (re)planted, it may absorb the active ingredient.

Suitable seeds are seeds of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize/sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the mixtures according to the invention may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.

For example, the active mixtures can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S. Pat. No. 5,013,659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259),

Furthermore, the mixtures according to the present invention can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).

The seed treatment application of the mixtures is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.

In the treatment of seeds the corresponding formulations are applied by treating the seeds with an effective amount of the mixture according to the present invention. Herein, the application rates of the active compound(s) are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 2.5 kg per 100 kg of seed. For specific crops such as lettuce the rate can be higher.

Compositions, which are especially useful for seed treatment are e.g.:

A Soluble concentrates (SL, LS)

D Emulsions (EW, EO, ES) E Suspensions (SC, OD, FS)

F Water-dispersible granules and water-soluble granules (WG, SG) G Water-dispersible powders and water-soluble powders (WP, SP, WS)

H Gel-Formulations (GF)

I Dustable powders (DP, DS)

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pre-germinated the latter

In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient(s), 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient(s), from 0.1 to 20% by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5% by weight of a wetter and from 0.5 to 15% by weight of a dispersing agent, up to 20% by weight, e.g. from 5 to 20% of an anti-freeze agent, from 0 to 15% by weight, e.g. 1 to 15% by weight of a pigment and/or a dye, from 0 to 40% by weight, e.g. 1 to 40% by weight of a binder (sticker/adhesion agent), optionally up to 5% by weight, e.g. from 0.1 to 5% by weight of a thickener, optionally from 0.1 to 2% of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1% by weight and a filler/vehicle up to 100% by weight.

Seed Treatment formulations may additionally also comprise binders and optionally colorants.

Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinyl pyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

The invention also relates to seed comprising mixtures according to the present invention. The amount of the compound I or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed.

Animal Health

The mixtures of the present invention are in particular also suitable for being used for combating parasites in and on animals.

An object of the present invention is therefore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.

The invention also relates to compositions containing a parasiticidally effective amount of compounds of formula I or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.

The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of mixture of the present invention or a composition comprising it.

The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a mixture of the present invention or a composition comprising it.

Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.

Surprisingly it has now been found that mixtures of the present invention are suitable for combating endo- and ectoparasites in and on animals.

Mixtures of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.

Mixtures of the present invention and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.

Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas.

The mixtures of the present invention and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.

The mixtures of the present invention are especially useful for combating ectoparasites.

The mixture of the present invention are especially useful for combating parasites of the following orders and species, respectively:

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, cockroaches (Blattaria—Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis, flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus gallinae, Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp, Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus, Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp, Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp,

Roundworms Nematoda:

Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp, Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp, Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus, Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale, Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi, Camallanida, e.g. Dracunculus medinensis (guinea worm) Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp., Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp,

Planarians (Plathelminthes):

Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp, Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.

The mixtures of the present invention and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.

Moreover, the use of mixtures of the present invention and compositions containing them for combating mosquitoes is especially preferred.

The use of mixtures of the present invention and compositions containing them for combating flies is a further preferred embodiment of the present invention.

Furthermore, the use of the mixtures of the present invention and compositions containing them for combating fleas is especially preferred.

The use of the mixtures of the present invention and compositions containing them for combating ticks is a further preferred embodiment of the present invention.

The mixtures of the present invention also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).

Administration can be carried out both prophylactically and therapeutically.

Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.

For oral administration to warm-blooded animals, the mixtures of the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the mixtures of the present invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.

Alternatively, the mixtures of the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the mixtures of the present invention may be formulated into an implant for subcutaneous administration. In addition the formula I compound may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the active compounds.

The mixtures of the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the active compounds. In addition, the active compound mixtures may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

Suitable preparations are:

-   -   Solutions such as oral solutions, concentrates for oral         administration after dilution, solutions for use on the skin or         in body cavities, pouring-on formulations, gels;     -   Emulsions and suspensions for oral or dermal administration;         semi-solid preparations;     -   Formulations in which the active compound is processed in an         ointment base or in an oil-in-water or water-in-oil emulsion         base;     -   Solid preparations such as powders, premixes or concentrates,         granules, pellets, tablets, boluses, capsules; aerosols and         inhalants, and active compound-containing shaped articles.

Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.

Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.

The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.

Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.

Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.

It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.

Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above.

Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.

Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.

Suitable solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-diox-olane and glycerol formal.

Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either of the water-in-oil type or of the oil-in-water type.

They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.

Suitable hydrophobic phases (oils) are:

liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length C₈-C₁₂ or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the C₈-C₁₀ fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C₁₆-C₁₈, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C₁₂-C₁₈, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.

Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.

Suitable emulsifiers are:

non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.

Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.

Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.

Liquid suspending agents are all homogeneous solvents and solvent mixtures.

Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.

For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.

Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.

In general, “parasiticidally effective amount” means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.

The compositions which can be used in the invention can comprise generally from about 0.001 to 95 wt % of the active compounds of the mixtures of the present invention.

Generally it is favorable to apply the active compounds of the mixtures of the present invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.

Ready-to-use preparations contain the active compounds of the mixtures of the present invention acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight.

Preparations which are diluted before use contain the active compounds of the mixtures of the present invention acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight.

Furthermore, the preparations comprise the active compounds of the mixtures of the present invention against endoparasites in concentrations of 10 ppm to 2 percent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.

In a preferred embodiment of the present invention, the compositions comprising the mixtures of the present invention are applied dermally/topically.

In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.

Generally it is favorable to apply solid formulations which release the active compounds of the mixtures of the present invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.

For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula I. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.

EXAMPLES

The present invention is now illustrated in further details by the following specific examples.

Some of the preferred compound examples are characterized by their physical data in the following table C. The characterization can be done by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), by NMR or by their melting points.

Some compounds were characterized by ¹H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: M=multiplett, q=quartett, t=triplett, d=doublet and s=singulett.

Alternatively the compounds were additionally or instead characterized by their melting point.

Specific compound examples of aminothiazoline compounds of formula I:

TABLE C Compound melting point ¹H NMR (in CDCl₃): example Structure of compound I F_(p) [° C.] δ [ppm] C.1

111.00-114.00 C.2

135.00-139.00 C.3

150.00-151.00 C.4

CDCl₃: 2.2-2.35 (m), 2.85-3.0 (m), 3.2 (t), 3.9 (t), 5.05 (mc), 6.65 (s), 6.8 (s), 6.9-7.1 (m) C.5

CDCl₃: 2.25 (s), 2.85-3.1 (m), 3.25 (mc), 3.9 (mc), 5.15 (mc), 6.65 (s), 6.8-7.05 (m) C.6

120.00-121.00 C.7

143.00-146.00 C.8

CDCl₃: 2.2 (s), 3.0 (mc), 3.2 (mc), 3.7 (s), 3.8 (s), 3.9 (mc), 5.1 (mc), 6.6-6.85 (m) C.9

CDCl₃: 2.25 (s), 3.05 (mc), 3.25 (mc), 3.7 (s), 3.8 (s), 3.9 (mc), 5.05 (mc), 6.6-7.1 (m) C.10

CDCl₃: 2.25 (s), 3.0 (mc), 3.25 (mc), 3.9 (mc), 5.15 (mc), 6.65 (s), 6.85 (s), 6.95 (mc), 7.3 (mc) C.11

CDCl₃: 2.25 (s), 2.55-2.8 (m), 3.15 (mc), 3.65 (mc), 3.8 (s), 5.2 (mc), 6.8 (s), 6.9 (mc), 7.2-7.4 (m) C.12

169.00-171.00 C.13

d6-DMSO: 2.3 (s), 2.6-2.9 (m), 3.1 (mc), 3.65 (mc), 3.75 (s), 5.1 (mc), 6.8 (mc), 6.95-7.2 (m), 7.45 (mc) C.14

d6-DMSO: 2.3 (s), 2.65-2.85 (m), 3.1 (mc), 3.65 (mc), 3.75 (s), 5.2 (mc), 6.9-7.3 (m) C.15

137.00-141.00 C.16

121.00-123.00 C.17

141.00-143.00 C.18

126.00-129.00 C.19

146.00-150.00 C.20

131.00-132.00 C.21

131.00-136.00 C.22

144.00-147.00 C.23

93.00-96.00 C.24

CDCl₃: 2.2 (s), 2.25 (s), 2.6 (s), 2.9-3.1 (m), 3.95-4.15 (m), 4.6 (mc), 6.6 (s), 6.8 (s), 7.3 (t), 7.55 (d), 7.65 (d) C.25

138.00-140.00 C.26

CDCl₃: 1.05 (s), 2.25 (s), 2.85-3.15 (m), 4.05 (mc), 4.9 (mc), 6.75 (s), 6.85 (s), 7.2 (mc), 7.35 (mc) C.27

CDCl₃: 2.25 (s), 2.8-3.1 (m), 3.5 (s), 3.95-4.2 (m), 4.55 (d), 4.7 (d), 4.85 (mc), 6.65 (s), 6.85 (s), 7.2 (t), 7.3 (d), 7.4 (d) C.28

91.00-94.00 C.29

CDCl₃: 1.05 (s), 2.2 (br s), 2.9-3.1 (m), 4.05 (mc), 4.6 (mc), 6.6 (s), 6.8 (s), 7.3 8 t), 7.55 (d), 7.7 (d) C.30

CDCl₃: 2.25 (s), 2.3 (s), 2.95 (mc), 3.1 (mc), 3.95-4.2 (m), 4.5-4.7 (m), 6.6 (s), 6.85 (s), 7.3 (t), 7.55 (d), 7.6 (d) C.31

d6-DMSO: 2.2 (s), 2.5 (s), 2.95 (mc), 3.05 (mc), 3.8-4.0 (m), 4.4 (mc), 5.9 (s), 6.0 (s), 6.7-6.8 (m) C.32

CDCl₃: 1.2 (t), 2.2 (s), 2.3 (s), 2.9-3.1 (m), 3.95-4.2 (m), 4.6 (mc), 6.6 (s), 6.85 (s), 7.3 (t), 7.55 (d), 7.65 (d) C.33

127.00-132.00 C.34

139.00-142.00 C.35

174.00-177.00 C.36

145.00-148.00 C.37

127.00-133.00 C.38

144.00-145.00 C.39

154.00-158.00 C.40

127.00-129.00 C.41

165.00-167.00 C.42

173.00-174.00 C.43

92.00-93.00

Specific Synthesis Examples of Compounds of Formula I S.1 Preparation of (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.33 of table C] S.1.a) Preparation of intermediate compound 2-(3,5-dimethylphenyl)-1-(2,3-dimethylphenyl)-ethylamine

Step 1: Preparation of 3,5-dimethylbenzyl magnesium chloride: To a mixture of 12.8 g magnesium turnings in 100 ml of anhydrous THF (tetrahydrofuran) was added under nitrogen atmosphere 0.3 ml ethyl bromide as starter reagent and the reaction was heated to 50° C. A solution of 67.8 g 3,5-dimethylbenzyl chloride in 450 ml of anhydrous THF was added slowly so that the reaction proceeded without violent reaction but with clear consumption. After the addition of the total amount of chloride, the solution was heated at 50° C. overnight. This resulted in a clear, greenish solution of 3,5-dimethylbenzyl magnesium chloride. This solution was used for the next step.

Step 2: A solution of 2,3-dimethylbenzaldehyde (50.0 g) in 200 ml of THF was treated at room temperature with a solution of lithium hexamethyl disilazane (LiHMDS) in toluene (410 ml, 1.0 M-solution, 1.1 equivalent) dropwise and the stirring was continued for 1.5 hours.

-   -   To this solution was added the solution of 3,5-dimethylbenzyl         magnesium chloride prepared as described above dropwise.         Stirring was continued afterwards for 2 hours at 35° C.     -   The reaction was quenched by the cautious addition of 300 ml of         potassium carbonate solution (5 wt % in water), extracted three         times with diethyl ether and the combined organic phases were         washed with water, dried over sodium sulphate and the solvent         evaporated. The residue was purified on silica gel with a         gradient of petrol ether/ethyl acetate and methanol/ethyl         acetate. This yielded 78 g (83%) of the title compound         2-(3,5-dimethylphenyl)-1-(2,3-dimethylphenyl)-ethylamine as a         yellowish oil.

S.1.b) Preparation of intermediate compound [2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-isothiocyanate

A solution of thiophosgene (39.5 g) in 200 ml of chloroform was treated with a solution of potassium carbonate (99 g) in water (200 ml) at room temperature. To this mixture was added a solution of 2-(3,5-dimethylphenyl)-1-(2,3-dimethylphenyl)-ethylamine (72.5 g) in chloroform (600 ml) with vigorous stirring. After completion of the reaction the mixture was poured into dichloromethane (500 ml) and washed three times with water, dried over sodium sulphate and the solvent evaporated in vacuo. This yielded the title compound [2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-isothiocyanate in form of a yellow oil (81.9 g).

S.1.c) Preparation of intermediate compound 1-[2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-3-(2-hydroxy-ethyl)-thiourea

To a solution of [2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-isothiocyanate (81.9 g) in chloroform (1 l) was added ethanolamine (25.4 g) dropwise at room temperature. The mixture was stirred for 3 hours and the solvent evaporated, the remainder dissolved in ethyl acetate and washed 6 times with water. The solution was dried over sodium sulphate. Removal of the solvent in vacuo yielded the 1-[2-(3,5-Dimethylphenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-3-(2-hydroxy-ethyl)-thiourea (94.8 g) as an off-white powder.

S.1.d) Preparation of (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.33 of table C]

A mixture of the above 1-[2-(3,5-Dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-3-(2-hydroxy-ethyl)-thiourea (94.7 g) and concentrated hydrochloric acid (700 ml) was heated under reflux for 2 hours. The hydrochloric acid phase was decanted carefully and the remainder dissolved in ethyl acetate and thoroughly washed three times with potassium carbonate solution (5 wt % in water), three times with water and dried over sodium sulphate. The solvent was removed by evaporation and the remainder titurated with a solution of light petrol ether/ethyl acetate (20/1), filtrated to yield the product (4,5-dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.33 of table C] as an off-white solid (67.1 g)

S.2 Preparation of (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.23 of table C]

S.2.d) A solution of [1-(2,3-dichlorophenyl)-2-(3,5-dimethylphenyl)-ethyl]-(4,5-dihydro-thiazol-2-yl)-amine (60.1 g, prepared accordingly to the preparation described above for specific compound example C.33, using 2,3-dichlorobenzaldehyde in Step 2) in dimethyl formamide (600 ml) was treated with potassium carbonate (32.8 g) and heated up to 60° C. A solution of acetyl chloride (14.9 g) in dimethyl formamide (100 ml) was added drop by drop and stirred for 5 hours at the same temperature. Stirring was continued overnight at room temperature, dimethyl formamide removed in vacuo and the remainder dissolved in ethyl acetate, washed once with water and three times with potassium carbonate solution (5 wt % in water), again with water and the organic phase dried over sodium sulphate. Evaporation of the solvent yielded (4,5-Dihydro-thiazol-2-yl)-[2-(3,5-dimethyl-phenyl)-1-(2,3-dimethyl-phenyl)-ethyl]-amine [specific compound example C.23 of table C] as a viscous oil (65.6 g) that crystallized upon standing.

Biology

Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):

$E = \frac{XY}{100}$

When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

The following tests demonstrates the control efficacy of compounds, mixtures or compositions of this invention on specific pests. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests.

The analysis of synergism or antagonism between the mixtures or compositions was determined using Colby's equation. Synergy was demonstrated with Compound C.33 of table C:

Test B.1

For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.

The compounds or mixtures were formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, the leaf disks were air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at 23±1° C., 50±5% RH (relative humidity) for 5 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in table B.1.

TABLE B.1 Average Vetch Aphid ppm Control % Abamectin + compound 0 + 0.8 0 C.33 0.08 + 0   0 0.08 + 0.8   75* Thiamethoxam + 0 + 0.8 0 compound C.33 0.08 + 0   0 0.08 + 0.8   100*  Fipronil + compound 0 + 0.8 0 C.33 2 + 0   25  2 + 0.8 75* *synergistic control effect according to Colby's equation

Test B.2

For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

The compounds or mixtures were formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at 23±1° C., 50±5% RH for 3 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in table B.2.

TABLE B.2 Average Green Peach Aphid ppm Control % Pymetrozine + compound   0 + 0.8  0 C.33 40 + 0  50  40 + 0.8  75* Pyridaben + compound  0 + 20  0 C.33 40 + 0   0 40 + 20 100* Abamectin + compound 0 + 4  0 C.33 0.08 + 0    0 0.08 + 4   100* Alphacypermethrin + 0 + 4  0 compound C.33 10 + 0  50 10 + 4   75* Chlorantraniliprole + 0 + 4  0 compound C.33 0.4 + 0   50 0.4 + 4   100* Thiamethoxam + test  0 + 20 50 compound 0.08 + 0    0 0.08 + 20    75* Fipronil + compound  0 + 20  0 C.33 0.4 + 0    0 0.4 + 20  100* *synergistic control effect according to Colby's equation

Further test systems which can be used for evaluating synergistic effects are e.g.

Test B.3

For evaluating control of boll weevil (Anthonomus grandis) the test unit consists of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.

The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 20 μl, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

After application, microtiter plates are incubated at 23±1° C., 50±5% RH for 5 days. Egg and larval mortality is visually assessed.

Test B.4

For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consists of 96-well-microtiter plates containing an insect diet and 50-80 C. capitata eggs.

The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 5 μl, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.

Test B.5

For evaluating control of tobacco budworm (Heliothis virescens) the test unit consists of 96-well-microtiter plates containing an insect diet and 15-25H. virescens eggs.

The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the insect diet at 10 μl, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

After application, microtiter plates are incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality is visually assessed.

Test B.6

For evaluating control of bird cherry aphid (Rhopalosiphum padi) through contact or systemic means the test unit consists of 96-well-microtiter plates containing barley leaf disks.

The compounds or mixtures are formulated using a solution containing 75 wt % water and 25 wt % DMSO. Different concentrations of formulated compounds or mixtures are sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, are mixed together.

After application, the leaf disks are air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids are then allowed to suck on the treated leaf disks and incubated at 25±1° C., 80±5% RH for 3 to 5 days. Aphid mortality and fecundity is visually assessed. 

1-37. (canceled)
 38. A pesticidal mixture comprising, 1) at least one compound I of formula I:

wherein R¹ is hydrogen, COCH₃, COCH₂OCH₃, COCH₂CH₃ or COCH₂C(CH₃)₃; R² is fluoro, chloro, bromo, CF₃, CH₃ or CH₃O, R³ is hydrogen, fluoro, chloro, bromo, CF₃ or CH₃, or R² and R³ form together with —OCF₂O— or —O—CH₂—O— a 5-membered fused heterocyclic ring; R⁴ is hydrogen, fluoro, chloro, bromo, CF₃, CH₃O or CH₃; R⁵, R⁶ are hydrogen, chloro, fluoro, bromo, CH₃, CH₃O or CF₃, wherein at least one of R⁵ or R⁶ is not hydrogen; or the tautomers, enantiomers, diastereomers or salts thereof, and 2) at least one active compound II selected from group A consisting of A.1 Acetylcholine esterase inhibitors triazemate or from the class of carbamates selected from the group consisting of aldicarb, alanycarb, benfuracarb, carbaryl, carbofuran, carbosulfan, methiocarb, methomyl, oxamyl, primicarb, propoxur and thiodicarb, or from the class of organophosphates selected from the group consisting of acephate, azinphos-ethyl, azinphos-methyl, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidaphos, methidathion, mevinphos, monocrotophos, oxymethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, pirimiphos-methyl, quinalphos, terbufos, tetrachlorvinphos, triazophos and trichlorfon; A.2 GABA-gated chloride channel antagonists selected from the group consisting of cyclodiene organochlorine endosulfan, N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon and N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon or from the class of phenylpyrazoles consisting of acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole and the phenylpyrazole compound II.A^(2.1):

A.3 Sodium channel modulators selected from the class of pyrethroids consisting of allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, permethrin, silafluofen and tralomethrin; A.4 Nicotinic acetylcholine receptor agonists/antagonists selected from the group consisting of nicotin, cartap hydrochloride, and thiocyclam or from the class of neonicotinoids consisting of acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam and AKD-1022; or the allosteric nicotinic acetylcholine receptor agonist spinosad; A.5 Chloride channel activators abamectin, emamectin benzoate, lepimectin or milbemectin; A.6 Juvenile hormone mimics hydroprene, kinoprene, fenoxycarb or pyriproxyfen; A.7 Compounds affecting the oxidative phosphorylation diafenthiuron, fenbutatin oxide, propargite or chlorfenapyr; A.8 Inhibitors of the chitin biosynthesis buprofezin or from the class of benzylureas consisting of bistrifluoron, diflubenzuron, flufenoxuron, hexaflumuron, lufenuron, novaluron and teflubenzuron; A.9 Moulting disruptors cyromazine or from the class of ecdysone agonists selected from the group consisting of methoxyfenozide, tebufenozide and azadirachtin; A.10 Mitochondrial electron transport inhibitors pyridaben, tolfenpyrad or flufenerim; A.11 Voltage-dependent sodium channel blockers indoxacarb or metaflumizone; A.12 Inhibitors of the lipid synthesis spirodiclofen, spiromesifen or spirotetramat; A.13 group of various compounds selected from the group consisting of amidoflumet, amitraz, bifenazate, clofentezine, cyenopyrafen, cyflumetofen, etoxazole, flonicamid, flubendiamine, flupyrazophos, hexythiazox, piperonyl butoxide, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliprole, the anthranilamid compound II.A^(13.1)

and the sulfoximine compounds II.A^(13.2)

in synergistically effective amounts.
 39. The pesticidal mixture of claim 38, wherein in compound I of formula I, R¹ is hydrogen or COCH₃; R² is fluoro, chloro or CH₃; R³, R⁴ are independently from one another hydrogen, fluoro, chloro, CF₃ or CH₃; and R⁵, R⁶ are hydrogen or CH₃, wherein at least one of R⁵ or R⁶ is not hydrogen; or the tautomers, enantiomers, diastereomers or salts thereof.
 40. The pesticidal mixture of claim 38, wherein in compound I of formula I, R¹ is hydrogen; R², R³ are CH₃; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the tautomers, enantiomers, diastereomers or salts thereof.
 41. The pesticidal mixture of claim 38, wherein in compound I of formula I, R¹ is hydrogen; R², R³ are chloro; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the tautomers, enantiomers, diastereomers or salts thereof.
 42. The pesticidal mixture of claim 38, wherein in compound I of formula I, R¹ is COCH₃; R², R³ are CH₃; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the enantiomers, diastereomers or salts thereof.
 43. The pesticidal mixture of claim 38, wherein in compound I of formula I, R¹ is COCH₃; R², R³ are chloro; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the enantiomers, diastereomers or salts thereof.
 44. The pesticidal mixture of claim 38, wherein at least one active compound II is selected within group A.1 from triazemate or primicarb; within group A.2 from endosulfan, N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole or vaniliprole or the phenylpyrazole compound II.A^(23.1); within group A.3 from allethrin, bifenthrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, etofenprox, fenpropathrin, fenvalerate, flucythrinate, tau-fluvalinate, silafluofen or tralomethrin; within group A.4 from thiocyclam, actamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, AKD-1022 or spinosad; within group A.5 from abamectin, emamectin benzoate, lepimectin or milbemectin; within group A.7 from diafenthiuron; within group A.8 from buprofezin; within group A.10 from pyridaben or flufenerim; within group A.11 from indoxacarb or metaflumizone; within group A.12 from spirodiclofen, spiromesifen or spirotetramat; within group A.13 from amitraz, flonicamid, flubendiamine, pymetrozine, pyridalyl, pyrifluquinazon, chlorantraniliprole, the anthranil compound II.A^(13.1) or the sulfoximine compounds II.A^(13.2), II.A^(13.3) or II.A^(13.4).
 45. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.2 is N-Ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, N-Ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α.α.α-trifluoro-p-tolyl) hydrazon, acetoprole or fipronil.
 46. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.3 is alpha-cypermethrin or deltamethrin.
 47. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.4 is clothianidin, imidacloprid or thiamethoxam.
 48. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.5 is abamectin.
 49. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.7 is diafenthiuron.
 50. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.8 is buprofezin.
 51. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.10 is pyridaben or flufenerim.
 52. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.11 is metaflumizone.
 53. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.12 is spiromesifen or spirotetramat.
 54. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.13 is flonicamid.
 55. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.13 is pymetrozine or pyrifluquinazon.
 56. The pesticidal mixture of claim 38, wherein at least one active compound II selected from group A.13 is chlorantraniliprole, the anthranil compound II.A^(13.1) or the sulfoximine compounds II.A^(13.2), II.A^(13.3) or II.A^(13.4).
 57. The pesticidal mixture of claim 38, comprising the active compound I of the formula I and the active compound II in a weight ratio of from 500:1 to 1:100.
 58. A compound I of formula I:

wherein R¹ is hydrogen, COCH₃, COCH₂OCH₃, COCH₂CH₃ or COCH₂C(CH₃)₃; R² is fluoro, chloro, bromo, CF₃, CH₃ or CH₃O, R³ is hydrogen, fluoro, chloro, bromo, CF₃ or CH₃, or R² and R³ form together with —OCF₂O— or —O—CH₂—O— a 5-membered fused heterocyclic ring; R⁴ is hydrogen, fluoro, chloro, bromo, CF₃, CH₃O or CH₃; R⁵, R⁶ are hydrogen, chloro, fluoro, bromo, CH₃, CH₃O or CF₃, wherein at least one of R⁵ or R⁶ is not hydrogen; or the tautomers, enantiomers, diastereomers or salts thereof.
 59. The compound of claim 58, wherein R¹ is hydrogen; R², R³ are CH₃; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the tautomers, enantiomers, diastereomers or salts thereof.
 60. The compound of claim 58, wherein R¹ is hydrogen; R², R³ are chloro; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the tautomers, enantiomers, diastereomers or salts thereof.
 61. The compound of claim 58, wherein R¹ is COCH₃; R², R³ are CH₃; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the enantiomers, diastereomers or salts thereof.
 62. The compound of claim 58, wherein R¹ is COCH₃; R², R³ are chloro; R⁴ is hydrogen; and R⁵, R⁶ are CH₃; or the enantiomers, diastereomers or salts thereof
 63. A method for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a mixture of claim 38 in pesticidally effective amounts.
 64. A method for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or the soil or water in which the plant is growing, with a compound of claim 58 in pesticidally effective amounts.
 65. A method for controlling insects, arachnids or nematodes comprising contacting an insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a mixture of claim 38 in pesticidally effective amounts.
 66. A method for controlling insects, arachnids or nematodes comprising contacting an insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with a compound of claim 58 in pesticidally effective amounts.
 67. The method of claim 63, wherein said mixture is applied in an amount of from 5 g/ha to 2000 g/ha.
 68. The method of claim 64, wherein said compound is applied in an amount of from 5 g/ha to 2000 g/ha.
 69. A method for protection of seed comprising contacting the seeds with a mixture of claim 38 in pesticidally effective amounts.
 70. A method for protection of seed comprising contacting the seeds with a compound of claim 58 in pesticidally effective amounts.
 71. The method of claim 69 wherein said mixture is applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 72. Seed, comprising the mixture of claim 38 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 73. Seed, comprising the compound of claim 58 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 74. A method for protecting animals against infestation or infection by parasites which comprises administering to the animals a parasitically effective amount of said mixture of claim 38 to the animal in need thereof.
 75. A method for protecting animals against infestation or infection by parasites which comprises administering to the animals a parasitically effective amount of said compound of claim 58 to the animal in need thereof.
 76. A method for treating animals infestated or infected by parasites which comprises administering to the animals a parasitically effective amount of said mixture of claim 38 to the animal in need thereof.
 77. A pesticidal or parasiticidal composition, comprising a liquid or solid carrier and the mixture of claim
 38. 